Herbicidal cyclohexane-1,3-dione derivatives

ABSTRACT

The invention concerns novel compounds of the formula I ##STR1## wherein R 1  is selected from hydrogen, alkyl, alkenyl, alkynyl, substituted alkyl, acyl, alkylsulfonyl, benzenesulfonyl, substituted benzenesulfonyl, and an inorganic or organic cation; 
     R 2  is selected from alkyl, alkenyl, alkynyl, substituted alkyl, haloalkenyl and haloalkynyl; 
     R 3  is selected from alkyl, fluoroalkyl, alkenyl, alkynyl and phenyl; and 
     n is an integer chosen from 2 to 5. 
     The compounds are cereal selective herbicides and in further embodiments of the invention provides processes for the preparation of compounds of formula I, intermediates useful in the preparation of compounds of formula I, herbicidal compositions containing as active ingredient a compound of formula I, and processes for severely damaging or killing unwanted plants by applying to the plants or to the growth medium of the plants an effective amount of a compound of formula I.

This invention relates to organic compounds having biological activityand in particular to organic compounds having herbicidal properties, toprocesses for the preparation of such compounds, to intermediates usefulin the preparation of such compounds and to herbicidal compositions andprocesses utilizing such compounds.

The use of certain cyclohexane-1,3-dione derivatives as grass herbicidesis known in the art. For example, the "Pesticide Manual" (C R WorthingEditor, The British Crop Protection Council, 6th Edition 1979) describesthe cyclohexane-1,3-dione derivative known commercially asalloxydim-sodium (methyl3-[1-allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocylcohex-3-ene-carboxylate)and its use as a grass herbicide. This compound is disclosed inAustralian Pat. No. 464 655 and its equivalents such as U.K. Pat. No. 1461 170 and U.S. Pat. No. 3,950,420.

More recently, at the 1980 British Crop Protection Conference ("1980British Crop Protection Conference--Weeds, Proceedings Vol 1, ResearchReports", pp 39 to 46, British Crop Protection Council, 1980), a newcyclohexane-1,3-dione grass herbicide code named NP 55(2-(N-ethoxybutrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one)was announced. This compound is disclosed in Australian PatentApplication No. AU-Al-35,314/78 and its equivalents.

As indicated above, both alloxydim-sodium and NP 55 are grassherbicides, that is, herbicides which selectively control the growth ofgrass weeds (monocotyledonous plants) in broad-leaved crops(dicotyledonous plants).

At the 1978 International Union of Pure and Applied Chemistry FourthInternational Congress of Pesticide Chemistry ("Advances in PesticideScience-Part 2", pp 235-243, Pergamon Press, 1979), in a paperdiscussing the chemical structure and herbicidal activity ofalloxydim-sodium, Iwataki and Hirono made the following disclosure aboutthe herbicidal selectivity between wheat and oats of certain 5-phenylsubstituted cyclohexane-1,3-dione derivatives:

"When substituted phenyl groups were introduced at the C-5 position(Table 6), the selectivity between wheats and oats such as Avena fatuaand Avena sativa was observed. The selectivity was found only in thecase of para-substituents at the phenyl nucleus and the effect was notfound in the case of di- or tri- substitution. Even in thepara-substituents, the degree of activity or selectivity was different.The best result was obtained when the methyl group was introduced at thepara-position and the hydroxy or the methoxy derivative gave moderatelygood results."

It has now been found that certain 5-phenyl substitutedcyclohexane-1,3-dione derivatives in which the phenyl ring issubstituted with more than one methyl group exhibit particularly usefulcereal selective herbicidal activity.

Accordingly the invention provides a compound of formula I: ##STR2##wherein: R¹ is chosen from the group consisting of: hydrogen; C₁ to C₆alkyl; C₂ to C₆ alkenyl; C₂ to C₆ alkynyl; substituted C₁ to C₆ alkylwherein the alkyl group is substituted with a substituent chosen fromthe group consisting of C₁ to C₆ alkoxy, C₁ to C₆ alkylthio, (C₁ to C₆alkoxy)carbonyl, phenyl and substituted phenyl wherein the benzene ringis substituted with from one to three substituents chosen from the groupconsisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl,C₁ to C₆ alkoxy and C₁ to C₆ alkylthio; C₁ to C₆ (alkyl) sulfonyl;benzene sulfonyl; substituted benzenesulfonyl wherein the benzene ringis substituted with from one to three substituents chosen from the groupconsisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl,C₁ to C₆ alkoxy and C₁ to C₆ alkylthio; an acyl group; and an inorganicor organic cation;

R² is chosen from the group consisting of: C₁ to C₆ alkyl; C₂ to C₆alkenyl; C₂ to C₆ haloalkenyl; C₂ to C₆ alkynyl; C₂ to C₆ haloalkynyl;substituted C₁ to C₆ alkyl wherein the alkyl group is substituted with asubstituent chosen from the group consisting of halogen, C₁ to C₆alkoxy, C₁ to C₆ alkylthio, phenyl and substituted phenyl wherein thebenzene ring is substituted with from one to three substituents chosenfrom the group consisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio;

R³ is chosen from the group consisting of: C₁ to C₆ alkyl; C₁ to C₆fluoroalkyl; C₂ to C₆ alkenyl; C₂ to C₆ alkynyl; and phenyl; and

n is an integer chosen from 2 to 5.

When in the compound of formula I R¹ is chosen from acyl the nature ofthe acyl group is not narrowly critical. Although not intending to bebound by theory, it is believed that when R¹ is acyl the acyl group isremoved in the plant by hydrolysis to give the corresponding compound offormula I in which R¹ is hydrogen. Suitable acyl groups include:alkanoyl, for example C₂ to C₆ alkanoyl; aroyl, for example benzoyl andsubstituted benzoyl wherein the benzene ring is substituted with fromone to three substituents chosen from the group consisting of halogen,nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁to C₆ alkylthio; and heteroaroyl, for example 2-furoyl, 3-furoyl,2-thenoyl and 3-thenoyl.

When in the compound of formula I R¹ is chosen from an inorganic ororganic cation the nature of the cation is not narrowly critical.Although not intending to be bound by theory, it is believed that whenR¹ is a cation the cation is removed in the plant to give a compound offormula I wherein R¹ is hydrogen. Suitable inorganic cations include thealkali and alkaline earth metal ions, heavy metal ions including thetransition metal ions, and the ammonium ion. Suitable organic cationsinclude the cation R⁴ R⁵ R⁶ R⁷ N.sup.⊕ wherein R⁴, R⁵, R⁶ and R⁷ areindependently chosen from the group consisting of: hydrogen; C₁ to C₁₀alkyl; substituted C₁ to C₁₀ alkyl wherein the alkyl group issubstituted with a substituent chosen from the group consisting ofhydroxy, halogen and C₁ to C₆ alkoxy; phenyl; benzyl; and the groupssubstituted phenyl and substituted benzyl wherein the benzene ring issubstituted with from one to three substituents chosen from the groupconsisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl,C₁ to C₆ alkoxy and C₁ to C₆ alkylthio.

It should be recognized that when R¹ is hydrogen the compounds of theinvention may exist in any one of three tautomeric forms as shown below:##STR3##

Suitable R¹ include hydrogen, C₁ to C₆ alkyl, C₂ to C₆ alkenyl, C₂ to C₆alkynyl, C₂ to C₆ alkanoyl, C₁ to C₆ alkyl substituted with C₁ to C₆alkoxy, C₁ to C₆ alkylthio, phenyl or substituted phenyl wherein thebenzene ring is substituted with from one to three substituents chosenfrom the group consisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio, benzoyl orsubstituted benzoyl wherein the benzene ring is substituted with fromone to three substituents chosen from the group consisting of halogen,nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁to C₆ alkylthio, C₁ to C₆ (alkyl)sulfonyl and benzenesulfonyl orsubstituted benzenesulfonyl wherein the benzene ring is substituted withfrom one to three substituents chosen from the group consisting ofhalogen, nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆alkoxy and C₁ to C₆ alkylthio, and the group M wherein M is an alkalimetal ion.

Suitable R² include C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₂ to C₆alkenyl, C₂ to C₆ alkynyl and C₁ to C₆ alkyl substituted with C₁ to C₆alkoxy, C₁ to C₆ alkylthio, phenyl or substituted phenyl wherein thebenzene ring is substituted with from one to three substituents chosenfrom the group consisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio.

Suitable R³ include C₁ to C₆ alkyl, C₂ to C₆ alkenyl and C₂ to C₆alkynyl.

Preferred R¹ include: hydrogen; C₂ to C₆ alkanoyl; benzoyl andsubstituted benzoyl wherein the benzene ring is substituted with from 1to 3 substituents selected from the group consisting of halogen, nitro,C₁ to C₆ alkyl and C₁ to C₆ alkoxy; and an inorganic or organic cationselected from the alkali metal ions, the alkaline earth metal ions,transition metal ions and the ammonium ion R⁴ R⁵ R⁶ R⁷ N.sup.⊕ whereinR⁴, R⁵, R⁶ and R⁷ are independently selected from the group consistingof hydrogen, C₁ to C₁₀ alkyl and substituted C₁ to C₁₀ alkyl wherein thealkyl group is substituted with a substituent selected from the groupconsisting of hydroxy and C₁ to C₆ alkoxy.

More preferred R¹ include hydrogen, acetyl, tertiary-butyryl, benzoyl,halobenzoyl, methylbenzoyl, methoxybenzoyl, nitrobenzoyl,trimethylbenzoyl, dinitrobenzoyl, the cations of the alkali metalssodium and potassium; the cations of the alkaline earth metalsmagnesium, calcium and barium, the cations of the transition metalsmanganese, copper, zinc, iron, nickel, cobalt and silver, the ammoniumion, and the tri- and tetra-alkyl ammonium ions wherein alkyl isselected from C₁ to C₆ alkyl and C₁ to C₆ hydroxyalkyl.

Even more preferred R¹ include hydrogen, benzoyl, sodium and potassium.

Preferred R² include: C₁ to C₆ alkyl; C₂ to C₆ alkenyl; C₂ to C₆alkynyl; C₁ to C₆ haloalkyl; C₂ to C₆ haloalkenyl; C₁ to C₆ alkylsubstituted with C₁ to C₆ alkoxy; C₁ to C₆ alkyl substituted with C₁ toC₆ alkylthio; and benzyl and substituted benzyl wherein the benzene ringis substituted with from one to three substituents selected from thegroup consisting of halogen, nitro and C₁ to C₆ alkyl.

More preferred R² include ethyl, n-propyl, n-butyl, allyl, propargyl,2-fluoroethyl, 2-chloroallyl, methylthiomethyl, benzyl, halobenzyl,methylbenzyl and nitrobenzyl.

Even more preferred R² include ethyl, n-propyl and allyl.

Preferred R³ include C₁ to C₆ alkyl. More preferred R³ include methyl,ethyl and n-propyl. Even more preferred R³ include ethyl and n-propyl.

Preferred n is an integer selected from 3 to 5.

Particularly preferred compounds of the invention include thosecompounds of formula I in which the benzene ring is substituted in atleast the 2-, 4- and 6-positions with methyl groups.

Specific examples of the compounds of the invention include thosecompounds detailed in Table 1 below.

                  TABLE 1                                                         ______________________________________                                         ##STR4##                      I                                              Com-                                                                          pound                                                                         No    (CH.sub.3).sub.n                                                                          R.sup.1   R.sup.2    R.sup.3                                ______________________________________                                        1     2,3-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        2     2,4-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        3     2,5-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        4     2,6-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        5     3,4-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        6     3,5-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        7     2,4,6-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        8     2,4,5-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        9     2,3,5,6-(CH.sub.3).sub.4                                                                  H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        10    2,3,4,6-(CH.sub.3).sub. 4                                                                 H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        11    3,4-(CH.sub.3).sub.2                                                                      COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        12    3,4-(CH.sub.3).sub.2                                                                      COCH.sub.3                                                                              C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        13    2,5-(CH.sub.3).sub.2                                                                      COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        14    2,3-(CH.sub.3).sub.2                                                                      COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        15    2,4,6-(CH.sub.3).sub.3                                                                    COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        16    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 CHCH.sub.2                                                                      n-C.sub.3 H.sub.7                      17    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 CHCH.sub.2                                                                      C.sub.2 H.sub.5                        18    2,4,6-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      19    2,4,6-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          CH.sub.3                               20    2,4,6-(CH.sub.3).sub.3                                                                    H         n-C.sub.3 H.sub.7                                                                        C.sub.2 H.sub.5                        21    2,4,6-(CH.sub.3).sub.3                                                                    H         n-C.sub.4 H.sub.9                                                                        C.sub.2 H.sub.5                        22    2,4,6-(CH.sub.3).sub.3                                                                    H         a          C.sub.2 H.sub.5                        23    2,4,6-(CH.sub.3).sub.3                                                                    H         b          C.sub.2 H.sub.5                        24    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 CCH                                                                             C.sub.2 H.sub.5                        25    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 CH.sub.2 F                                                                      C.sub.2 H.sub.5                        26    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 C(Cl)CH.sub.2                                                                   C.sub.2 H.sub.5                        27    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 C.sub.6 H.sub.5                                                                 C.sub.2 H.sub.5                        28    2,4,6-(CH.sub.3).sub.3                                                                    H         c          C.sub.2 H.sub.5                        29    2,4,6-(CH.sub.3).sub.3                                                                    H         d          C.sub.2 H.sub.5                        30    2,4,6-(CH.sub.3).sub.3                                                                    H         e          C.sub.2 H.sub.5                        31    2,4,6-(CH.sub.3).sub.3                                                                    H         f          C.sub.2 H.sub.5                        32    2,4,6-(CH.sub.3).sub.3                                                                    H         g          C.sub.2 H.sub.5                        33    2,4,6-(CH.sub.3).sub.3                                                                    H         h          C.sub.2 H.sub.5                        34    2,4,6-(CH.sub.3).sub.3                                                                    H         i          C.sub.2 H.sub.5                        35    2,4,6-(CH.sub.3).sub.3                                                                    H         n-C.sub.4 H.sub.9                                                                        n-C.sub.3 H.sub.7                      36    2,4,6-(CH.sub.3).sub.3                                                                    H         a          n-C.sub.3 H.sub.7                      37    2,4,6-(CH.sub.3).sub.3                                                                    H         b          n-C.sub.3 H.sub.7                      38    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 CCH                                                                             n-C.sub.3 H.sub.7                      39    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 CH.sub.2 F                                                                      n-C.sub.3 H.sub.7                      40    2,4,6-(CH.sub.3).sub.3                                                                    H         CH.sub.2 C(Cl)CH.sub.2                                                                   n-C.sub.3 H.sub.7                      41    2,4,6-(CH.sub.3).sub.3                                                                    H         c          n-C.sub.3 H.sub.7                      42    2,4,6-(CH.sub.3).sub.3                                                                    H         d          n-C.sub.3 H.sub.7                      43    2,4,6-(CH.sub.3).sub.3                                                                    Na.sup.⊕                                                                            C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        44    2,4,6-(CH.sub.3).sub.3                                                                    j         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        45    2,4,6-(CH.sub.3).sub.3                                                                    k         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        46    2,4,6-(CH.sub.3).sub.3                                                                    l         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        47    2,4,6-(CH.sub.3).sub.3                                                                    Na.sup.⊕                                                                            CH.sub.2 CHCH.sub.2                                                                      C.sub.2 H.sub.5                        48    2,4,6-(CH.sub.3).sub.3                                                                    COC.sub.6 H.sub.5                                                                       CH.sub.2 CHCH.sub.2                                                                      C.sub.2 H.sub.5                        49    2,4,6-(CH.sub.3).sub.3                                                                    COC.sub.6 H.sub.5                                                                       CH.sub.2 CCH                                                                             C.sub.2 H.sub.5                        50    2,4,6-(CH.sub.3).sub.3                                                                    COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      51    2,4,6-(CH.sub.3).sub.3                                                                    COC.sub.6 H.sub. 5                                                                      CH.sub.2 CHCH.sub.2                                                                      n-C.sub.3 H.sub.7                      52    2,3,4-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        53    2,3,5-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        54    3,4,5-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        55    2,3,4,6-(CH.sub.3).sub.4                                                                  H         C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      56    2,3,4,6-(CH.sub.3).sub.4                                                                  H         CH.sub.2 CHCH.sub.2                                                                      C.sub.2 H.sub.5                        57    2,3,4,6-(CH.sub.3).sub.4                                                                  H         CH.sub.2 CHCH.sub.2                                                                      n-C.sub.3 H.sub.7                      58    2,3,4,6-(CH.sub.3).sub.4                                                                  COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        59    2,3,4,5-(CH.sub.3).sub.4                                                                  Na.sup.⊕                                                                            C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        60    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        61    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.2 CHCH.sub.2                                                                      C.sub.2 H.sub.5                        62    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      63    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.2 CHCH.sub.2                                                                      n-C.sub.3 H.sub.7                      64    2,3,4,5-(CH.sub.3).sub.4                                                                  H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub. 5                       65    3,4-(CH.sub.3).sub.2                                                                      H         n-C.sub.3 H.sub.7                                                                        C.sub.2 H.sub.5                        66    3,4-(CH.sub.3).sub.2                                                                      H         CH.sub.2 CHCH.sub.2                                                                      C.sub.2 H.sub.5                        67    3,4-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      68    3,4-(CH.sub.3).sub.2                                                                      H         n-C.sub.3 H.sub.7                                                                        n-C.sub.3 H.sub.7                      69    3,4-(CH.sub.3).sub.2                                                                      H         CH.sub.2 CHCH.sub.2                                                                      n-C.sub.3 H.sub.7                      70    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         C.sub.2 H.sub.5                                                                          CH.sub.3                               71    2,3,6-(CH.sub.3).sub.3                                                                    H         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        72    2,3,4,5,6-(CH.sub.3).sub.5                                                                Na.sup.⊕                                                                            C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      73    2,3,4,5,6-(CH.sub.3).sub.5                                                                COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      74    2,3,4,6-(CH.sub.3).sub.4                                                                  H         CH.sub.2 CH.sub.2 F                                                                      n-C.sub.3 H.sub.7                      75    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.2 CH.sub.2 F                                                                      n-C.sub.3 H.sub.7                      76    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.2 CH.sub.2 F                                                                      C.sub.2 H.sub.5                        77    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.3   n-C.sub.3 H.sub.7                      78    2,3,4,5,6-(CH.sub.3).sub.5                                                                Na.sup.⊕                                                                            C.sub.2 H.sub. 5                                                                         C.sub.2 H.sub.5                        79    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         n-C.sub.3 H.sub.7                                                                        n-C.sub.3 H.sub.7                      80    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.3   C.sub.2 H.sub.5                        81    2,3,4,5,6-(CH.sub.3).sub.5                                                                COC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        82    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.2 C(Cl)CH.sub.2                                                                   n-C.sub.3 H.sub.7                      83    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         a          C.sub.2 H.sub.5                        84    2,3,4,5,6-(CH.sub.3).sub.5                                                                1/2 Cu .sup.○2+                                                                  C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      85    2,3,4,5,6-(CH.sub.3).sub.5                                                                1/2 Ni .sup.○2+                                                                  C.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                      86    2,3,4,5,6-(CH.sub.3).sub.5                                                                H         CH.sub.2 SCH.sub.3                                                                       C.sub.2 H.sub.5                        87    2,5-(CH.sub.3).sub.2                                                                      H         C.sub.2 H.sub.5                                                                          C.sub.6 H.sub.5                        88    2,4,6-(CH.sub.3).sub.3                                                                   .sup.⊕ N(n-C.sub.4 H.sub.9).sub.4                                                    C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        89    2,4,6-(CH.sub.3).sub.3                                                                    m         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        90    2,4,6-(CH.sub.3).sub.3                                                                    n         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        91    2,4,6-(CH.sub.3).sub.3                                                                    o         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        92    2,4,6-(CH.sub.3).sub.3                                                                    p         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        93    2,4,6-(CH.sub.3).sub.3                                                                    CH.sub.3 CO                                                                             C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        94    2,4,6-(CH.sub.3).sub.3                                                                    q         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        95    2,4,6-(CH.sub.3).sub.3                                                                    r         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                        ______________________________________                                         Footnotes to Table 1                                                          a trans  CH.sub.2 CHCHCH.sub.3                                                b CH.sub.2 CH.sub.2 CHCH.sub.2                                                c CH.sub.2 C.sub.6 H.sub.4 Cl4                                                d CH.sub.2 C.sub.6 H.sub.4 Br4                                                e CH.sub.2 C.sub.6 H.sub.4 F4                                                 f CH.sub.2 C.sub.6 H.sub.4 CH.sub.34                                          g CH.sub.2 C.sub.6 H.sub.4 NO.sub.24                                          h CH.sub.2 C.sub.6 H.sub.4 Cl3                                                i CH.sub.2 C.sub.6 H.sub.3 Cl.sub.22,4                                        j COC.sub.6 H.sub.4 NO.sub.24                                                 k COC.sub.6 H.sub.4 NO.sub.23                                                 l COC.sub.6 H.sub.3 (NO.sub.2).sub.23,5                                       m COC.sub.6 H.sub.4 CH.sub.34                                                 n COC.sub.6 H.sub.2 (CH.sub.3).sub.32,4,6                                     o COC.sub.6 H.sub.4 OCH.sub.34                                                p COC.sub.6 H.sub.4 Cl4                                                       q COC(CH.sub.3).sub.3                                                         r CH.sub.2 COOCH.sub.2 CH.sub.3                                          

The compounds of the invention may be prepared by a variety of methodsand in a further aspect the the invention provides methods for thepreparation of compounds of formula I.

Conveniently the preparation of the compounds of the invention can beconsidered in three or four parts.

Part A involves the formation of a 5-(substitutedphenyl)cyclohexane-1,3-dione of formula IX. This reaction may be carriedout in a two step process by condensing a benzaldehyde derivative offormula V with acetone to form a ketone of formula VI, which is in turncondensed with a malonic acid ester of formula VII to give a5-(substituted phenyl)cyclohexane-1,3-dione of formula IX, either withor without the isolation of the intermediate of formula VIII.

Alternatively, this preparation may be carried out in a two step processby condensing a benzaldehyde derivative of formula V with a malonic acidester of formula VII to give a benzylidenemalonate derivative of formulaX which is in turn condensed with an acetoacetic acid ester of formulaXI to give a 5-(substituted phenyl)cyclohexane-1,3-dione of formula IX,either with or without isolation of the intermediate of formula XII.

In a further alternative process this preparation may be carried out bycondensing a cinnamate of formula XXI with an acetoacetic acid ester offormula XI to give a 5-(substituted phenyl)cyclohexane-1,3-dione offormula IX, either with or without isolation of the intermediate offormula VIII.

The above reaction sequences are set out in SCHEME A parts (i), (ii) and(iii) respectively below, wherein R represents a C₁ to C₆ alkyl group.##STR5##

Part B involves the acylation of a compound of formula IX to give a2-acyl-5-(substituted phenyl)cyclohexane-1,3-dione of formula XIII. Thisreaction may be carried out by reacting a 5-(substitutedphenyl)cyclohexane-1,3-dione of formula IX with:

(iv) a mixture of an acid anhydride of formula XIV and either a salt ofthat acid or an alkoxide salt wherein M is an alkali metal ion and R isC₁ to C₆ alkyl;

(v) a mixture of an acid anhydride of formula XIV and the correspondingacid;

(vi) an acid halide of formula XV;

(vii) a mixture of an acid halide of formula XV and the correspondingacid; or

(viii) an alkali metal or alkaline earth metal hydride following byreaction with an acid anhydride of formula XIV or an acid halide offormula XV.

Alternatively this reaction may be carried out by:

(ix) reacting a 5-(substituted phenyl)cyclohexane-1,3-dione of formulaIX with an acid halide of formula XV in the presence of pyridine to givean intermediate O-acyl derivative of formula XVI; and then:

(x) reacting the intermediate of formula XVI with a Lewis acid catalyst;

(xi) reacting the intermediate of formula XVI with the correspondingacid of the acid halide of formula XV; or

(xii) reacting the intermediate of formula XVI with imidazole.

Each of these reactions is outlined in SCHEME B below wherein halrepresents halogen. ##STR6##

Part C involves the formation of a compound of the invention of formulaI wherein R¹ is hydrogen, that is a compound of formula II. Thisreaction may be carried out either:

(xiii) by reacting a compound of formula XIII with an alkoxyaminederivative of formula XVII to give a compound of formula II; or

(xiv) by reacting a compound of formula XIII with hydroxylamine to givean intermediate oxime derivative of formula XVIII and reacting the oximederivative of formula XVIII with an alkylating agent of formula XIX togive a compound of formula II.

These reaction sequences are set out in SCHEME C below wherein L is agood leaving group such as, for example, chloride, bromide, iodide,sulfate, nitrate, methyl sulfate, ethyl sulfate, tetrafluoroborate,hexafluorophosphate, hexafluoroantimonate, methanesulfonate,fluorosulfonate, fluoromethanesulfonate and trifluoromethanesulfonate.##STR7##

Compounds of the invention of formula I wherein R¹ is an acyl or asulfonyl group may be prepared from compounds of the invention offormula I wherein R¹ is hydrogen, that is, compounds of formula II, byetherification, acylation, or sulfonylation as required. This reactionis outlined in SCHEME D below. ##STR8##

Compounds of the invention of formula I wherein R¹ is an inorganic ororganic cation may be prepared from the compounds of the invention offormula I wherein R¹ is hydrogen, that is, compounds of formula II, byreacting said compounds of formula II with an inorganic or organic salt.For example, the compounds of formula I werein R¹ is an alkalki metalion may be prepared by reacting the appropriate compound of formula IIwith the appropriate alkali metal hydroxide or alkoxylate. The compoundsof formula I wherein R¹ is a transition metal ion or an organic cationmay similarly be prepared by reacting the appropriate compound offormula II with an appropriate transition metal salt or organic base.Alternatively, the compounds of formula I wherein R¹ is a transitionmetal ion or an organic cation may be prepared by reacting theappropriate compound of formula I wherein R¹ is an alkali metal ion withan appropriate transition metal salt or organic salt.

Accordingly, in a further aspect the invention provides a process forthe preparation of a compound of formula I, wherein R¹, R² and R³ are ashereinbefore defined, which process comprises:

(a) reacting a benzaldehyde derivative of formula V with acetone to givea ketone derivative of formula VI and reacting the ketone derivative offormula VI with a malonic acid ester of formula VII, wherein R is C₁ toC₆ alkyl, to give a 5-(substituted phenyl)cyclohexane-1,3-dionederivative of formula IX; or reacting a benzaldehyde derivative offormula V with a malonic acid ester of formula VII to give abenzylidenemalonate derivative of formula X and reacting thebenzylidenemalonate derivative of formula X with an acetoacetic acidester of formula XI, wherein R is C₁ to C₆ alkyl, to give a5-(substituted phenyl)cyclohexane-1,3-dione derivative of formula IX; or

reacting a cinnamate of formula XXI, wherein R is C₁ to C₆ alkyl, withan acetoacetic acid ester of formula XI, wherein R is C₁ to C₆ alkyl, togive a 5-(substituted phenyl)cyclohexane-1,3-dione derivative of formulaIX;

(b) acylating the 5-(substituted phenyl)cyclohexane-1,3-dione derivativeof formula IX with an acid anhydride of formula XIV or an acid halide offormula XV to give a 2-acyl-5-(substituted phenyl)cyclohexane-1,3-dionederivative of formula XIII;

(c) reacting the 2-acyl-5-(substituted phenyl)cyclohexane-1,3-dionederivative of formula XIII with an alkoxyamine derivative of formulaXVII to give a compound of the invention of formula II or reacting the2-acyl-5-(substituted phenyl)cyclohexane-1,3-dione derivative of formulaXIII with hydroxylamine and alkylating the oxime intermediate of formulaXVIII with an alkylating agent of formula XIX, wherein L is a goodleaving group, to give a compound of the invention of formula II; andoptionally

(d) reacting the compound of the invention of formula II with a compoundof formula XX, wherein L is a good leaving group, or reacting thecompound of the invention of formula II with an inorganic or organicbase or salt, to give a compound of the invention of formula I.

Certain of the intermediate compounds of formulae VI, VIII, IX, X, XII,XXI, XIII, XVI and XVIII are novel compounds and therefore as a furtherembodiment the invention provides novel compounds of formulae VI, VIII,IX, X, XII, XXI, XIII, XVI and XVIII, wherein the substituents are ashereinbefore defined, and processes for the preparation thereof.

The compounds of formula I are active as herbicides againstmonocotyledonous weeds, wild grasses, and in particular are selectivelyactive against difficultly controllable wild grasses in crops ofcultivated plants. The compounds of the invention are especially usefulin the control of wild grasses such as wild oats and rye grass in cropsof cultivated monocotyledonous plants such as wheat, barley and othervarieties of cereals.

Accordingly, in yet a further aspect the invention provides a processfor controlling monocotyledonous weeds in cultivated crops, especiallywild grasses in cereal crops such as wheat and barley, which processcomprises applying to the crop, or to the growth medium of the crop, acompound of formula I, as hereinbefore defined, in an amount sufficientto severely damage or kill the weeds but insufficient to damage the cropsubstantially.

As hereinbefore indicated, certain cyclohexane-1,3-dione derivatives,such as those disclosed in Australian Pat. No. 464,655 and AustralianPatent Application No. 35,314/78 and numerous other patents and patentapplications, are known to be general grass herbicides which show nouseful cereal selectivity. Moreover, it is known from the teaching ofIwataki and Hirono ("Advances in Pesticides Science-Part 2", pp 235-243,Pergamon Press, 1979) that some cereal selectivity is observed in suchcyclohexane-1,3-dione derivatives when a phenyl group substituted in thepara-position is introduced into the 5-position of the cyclohexane ringbut that "The selectivity was found only in the case ofpara-substituents at the phenyl nucleus and that the effect was notfound in the case of di- or tri-substitution". Therefore, it iscompletely unexpected to find that the cyclohexane-1,3-dione derivativesof the present invention, which have, located in the 5-position of thecyclohexane ring, a phenyl group which is in turn substituted with fromtwo to five methyl groups, are cereal selective herbicides whicheffectively control monocotyledonous weeds such as wild oats and ryegrass in crops of sensitive, cultivated monocotyledonous plants such aswheat and barley. It is even more surprising to find that thosecyclohexane-1,3-dione derivatives of the present invention which have,located in the 5-position of the cyclohexane ring, a phenyl group whichis in turn substituted with methyl groups in at least the 2-, 4- and6-positions, are highly active against monocotyledonous weeds such aswild oats and rye grass at very low rates of application and at the sametime are very safe on wheat, a sensitive, cultivated monocytyledonousplant.

The compounds of formula I may be applied directly to the plant(post-emergence application) or to the soil before the emergence of theplant (pre-emergence application). However, the compounds are, ingeneral, more effective when applied to the plant post-emergence.

The compounds of formula I may be used on their own to inhibit thegrowth of, severely damage, or kill plants but are preferably used inthe form of a composition comprising a compound of the invention inadmixture with a carrier. Therefore, in yet a further aspect theinvention provides plant growth inhibiting, plant damaging, or plantkilling compositions comprising a compound of formula I as hereinbeforedefined and an inert carrier therefor.

The compositions of the present invention may be in the form of solids,liquids or pastes. The compositions include both dilute compositionswhich are ready for immediate use and concentrated compositions whichmay require dilution before use. Therefore, the concentration of theactive ingredient in the compositions of the present invention will varydepending on the type of formulation and whether the composition isready for use such as, for example, a dust formulation or an aqueousemulsion or whether the composition is a concentrate such as, forexample, an emulsifiable concentrate or a wettable powder, which issuitable for dilution before use. In general the compositions of thepresent invention comprise from 0.01% to 99% by weight of activeingredient.

The solid compositions may be in the form of powders, dusts, pellets,grains, and granules wherein the active ingredient is mixed with a soliddiluent. Powders and dusts may be prepared by mixing or grinding theactive ingredient with a solid carrier to give a finely dividedcomposition. Granules, grains and pellets may be prepared by bonding theactive ingredient to a solid carrier, for example, by coating orimpregnating the preformed granular solid carrier with the activeingredient or by agglomeration techniques.

Examples of solid carriers include: mineral earths and clays such as,for example, kaoline, bentonite, kieselguhr, Fuller's earth, Attaclay,diatomaceous earth, bole, loess, talc, chalk, dolomite, limestone, lime,calcium carbonate, powdered magnesia, magnesium oxide, magnesiumsulfate, gypsum, calcium sulfate, pyrophyllite, silicic acid, silicatesand silica gels; fertilizers such as, for example, ammonium sulfate,ammonium phosphate, ammonium nitrate and urea; natural products ofvegetable origin such as, for example, grain meals and flours, barkmeals, wood meals, nutshell meals and cellulosic powders; and syntheticpolymeric materials such as, for example, ground or powdered plasticsand resins.

Alternatively, the solid compositions may be in the form of dispersibleor wettable dusts, powders, granules or grains wherein the activeingredient and the solid carrier are combined with one or more surfaceactive agents which act as wetting, emulsifying and/or dispersing agentsto facilitate the dispersion of the active ingredient in liquid.

Examples of surface active agents include those of the cationic, anionicand non-ionic type. Cationic surface active agents include quaternaryammonium compounds, for example, the long chain alkylammonium salts suchas cetyltrimethylammonium bromide. Anionic surface active agentsinclude: soaps or the alkali metal, alkaline earth metal and ammoniumsalts of fatty acids; the alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid; the alkali metal, alkaline earthmetal and ammonium salts of arylsulfonic acids including the salts ofnaphthalenesulfonic acids such as butylnapththalenesulfonic acid, thedi- and tri-isopropylnaphthalenesulfonic acids, the salts of thecondensation products of sulfonated naphthalene and naphthalenederivatives with formaldehyde, the salts of the condensation products ofsulfonated naphthalene and naphthalene derivatives with phenol andformaldehyde, and the salts of alkylarylbenzenesulfonic acids such asdodecylbenzenesulfonic acid; the alkali metal, alkaline earth metal andammonium salts of the long chain mono esters of sulfuric acid oralkylsulfates such as laurylsulfate and the mono esters of sulfuric acidwith fatty alcohol glycol ethers. Nonionic surface active agentsinclude: the condensation products of ethylene oxide with fatty acoholssuch as oleyl alcohol and cetyl alcohol; the condensation products ofethylene oxide with phenols and alkylphenols such as isooctylphenol,octylphenol and nonylphenol; the condensation products of ethylene oxidewith castor oil; the partial esters derived from long chain fatty acidsand hexitol anhydrides, for example sorbitan monolaurate, and theircondensation products with ethylene oxide; ethylene oxide/propyleneoxide block copolymers; lauryl alcohol polyglycol ether acetal; and thelecithins.

The liquid compositions may comprise a solution or dispersion of theactive ingredient in a liquid carrier optionally containing one or moresurface active agents which act as wetting, emulsifying and/ordispersing agents. Examples of liquid carriers include: water; mineraloil fractions such as, for example, kerosene, solvent naphtha,petroleum, coal tar oils and aromatic petroleum fractions; aliphatic,cycloaliphatic and aromatic hydrocarbons such as, for example, paraffin,cyclohexane, toluene, the xylenes, tetrahydronaphthalene and alkylatednaphthalenes; alcohols such as, for example, methanol, ethanol,propanol, isopropanol, butanol, cyclohexanol and propylene glycol;ketones such as, for example, cyclohexanone and isophorone; and stronglypolar organic solvents such as, for example, dimethylformamide,dimethylsulfoxide, N-methylpyrrolidone and sulfolane.

A preferred liquid composition comprises an aqueous suspension,dispersion or emulsion of the active ingredient which is suitable forapplication by spraying, atomixing or watering. Such aqueouscompositions are generally prepared by mixing concentrated compositionswith water. Suitable concentrated compositions include emulsionconcentrates, pastes, oil dispersions, aqueous suspensions and wettablepowders. The concentrates are usually required to withstand storage forprolonged periods and after such storage to be capable of dilution withwater to form aqueous preparations which remain homogeneous for asufficient time to enable them to be applied by conventional sprayequipment. The concentrates conveniently contain from 20 to 99%,preferably 20 to 60%, by weight of active ingredient.

Emulsion or emulsifiable concentrates are conveniently prepared bydissolving the active ingredient in an organic solvent containing one ormore surface active agents. Pastes may be prepared by blending thefinely divided active ingredient with a finely divided solid carrier,one or more surface active agents and optionally an oil. Oil dispersionsmay be prepared by grinding together the active ingredient, ahydrocarbon oil, and one or more surface active agents. Aqueoussuspension concentrates may conveniently be prepared by ball milling amixture of the active ingredient, water, at least one surface activeagent and preferably at least one suspending agent. Suitable suspendingagents include: hydrophilic colloids such as, for example,poly(N-vinylpyrrolidone), sodium carboxymethylcellulose and thevegetable gums gum acacia and gum tragacanth; hydrated colloidal mineralsilicates such as, for example, montmorillonite, beidellite, nontronite,hectorite, saponite, sauconite and bentonite; other cellulosederivatives; and poly(vinyl alcohol). Wettable powder concentrates mayconveniently be prepared by blending together the active ingredient, oneor more surface active agents, one or more solid carriers and optionallyone or more suspending agents and grinding the mixture to give a powderhaving the required particle size.

The aqueous suspensions, dispersions or emulsions may be prepared fromthe concentrated compositions by mixing the concentrated compositionswith water optionally containing surface active agents and/or oils.

It should be noted that the compounds of the invention of formula Iwherein R¹ is hydrogen are acidic. Therefore, the compounds of formula Imay be formulated and applied as the salts of organic or inorganicbases. In formulating and employing the compounds of formula I in theform of their salts either the salts per se, that is the compounds offormula I wherein R¹ is an inorganic or an organic cation, may be usedin the formulation or the compounds of formula I wherein R¹ is hydrogenmay be used in the formulation and the salts generated in situ by theuse of the appropriate organic or inorganic base.

The mode of application of the compositions of the invention will dependto a large extent on the type of composition used and the facilitiesavailable for its application. Solid compositions may be applied bydusting or any other suitable means for broadcasting or spreading thesolid. Liquid compositions may be applied by spraying, atomizing,watering, introduction into the irrigation water, or any other suitablemeans for broadcasting or spreading the liquid.

The rate of application of the compounds of the invention will depend ona number of factors including, for example, the compound chosen for use,the identity of the plants whose growth is to be inhibited theformulations selected for use and whether the compound is to be appliedfor foliage or root uptake. As a general guide, however, an applicationrate of from 0.005 to 20 kilograms per hectare is suitable while from0.01 to 5.0 kilograms per hectare may be preferred.

The compositions of the invention may comprise, in addition to one ormore compounds of the invention, one or more compounds not of theinvention but which possess biological activity. For example, ashereinbefore indicated the compounds of the invention are in generalsubstantially more effective against monocotyledonous plants or grassspecies than against dicotyledonous plants or broad-leaved species. As aresult, in certain applications the herbicidal use of the compounds ofthe invention alone may not be sufficient to protect a crop. Accordinglyin yet a still further embodiment the invention provides a herbicidalcomposition comprising a mixture of at least one herbicidal compound offormula I as hereinbefore defined with at least one other herbicide.

The other herbicide may be any herbicide not having the formula I. Itwill generally be a herbicide having a complementary action. Forexample, one preferred class is of mixtures comprising a herbicideactive against broad-leaved weeds. A second preferred class is ofmixtures comprising a contact herbicide.

Examples of useful complementary herbicides include:

A. benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as3-isopropylbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide (common namebentazon);

B. hormone herbicides and in particular the phenoxyalkanoic acids suchas 4-chloro-2-methylphenoxy acetic acid (common name MCPA),2-(2,4-dichlorophenoxy)propionic acid (common name dichlorprop),2,4,5-trichlorophenoxyacetic acid (common name 2,4,5-T),4-(4-chloro-2-methylphenoxy)butyric acid (common name MCPB),2,4-dichlorophenoxyacetic acid (common name 2,4-D),4-(2,4-dichlorophenoxy)butyric acid (common name 2,4-DB),2-(4-chloro-2-methylphenoxy)propionic acid (common name mecoprop), andtheir derivatives (eg salts, esters, amides and the like);

C. 3-8 4-(4-halophenoxy)phenyl]-1,1-dialkylureas such as3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea (common namechloroxuron);

D. dinitrophenols and their derivatives (eg acetates) such as2-methyl-4,6-dinitrophenol (common name DNOC),2-tertiarybutyl-4,6-dinitrophenol (common name dinoterb),2-secondarybutyl-4,6-dinitrophenol (common name dinoseb) and its esterdinoseb acetate;

E. dinitroaniline herbicides such asN',N'-diethyl2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (commonname dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline(common name trifluralin) and4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (common name nitralin);

F. phenylurea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (common name diuron) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (common namefluometuron);

G. phenylcarbamoyloxyphenylcarbamates such as3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)carbamate (common namephenmedipham) and 3-[(ethoxycarbonyl)amino]phenyl phenylcarbamate(common name desmedipham);

H. 2-phenylpyridazin-3-ones such as5-amino-4-chloro-2-phenylpyridazin-3-one (common name pyrazon);

I. uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil (commonname lenacil), 5-bromo-3-sec-butyl-6-methyluracil (common name bromacil)and 3-tert-buty-5-chloro-6-methyluracil (common name terbacil);

J. triazine herbicides such as2-chloro-4-ethylamino-6-(iso-propylamino)-1,3,5-triazine (common nameatrazine), 2-chloro-4,6-di(ethylamino)-1,3,5-triazine (common namesimazine) and 2-azido-4-(iso-propylamino)-6-methylthio-1,3,5-triazine(common name aziproptryne);

K. 1-alkoxy-2-alkyl-3-phenylurea herbicides such as3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (common name linuron),3-(4-chlorophenyl)-1-methoxy-1-methylurea (common name monolinuron) and3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (common namechlorobromuron);

L. thiolcarbamate herbicides such as S-propyl dipropylthiocarbamate(common name verolate);

M. 1,2,4-triazin-5-one herbicides such as4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one (common namemetamitron) and4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,3,4-triazin-5-one(common name metribuzin);

N. benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid (commonname 2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (common namedicamba) and 3-amino-2,5-dichlorobenzoic acid (common name chloramben).

O. anilide herbicides such asN-butoxymethyl-α-chloro-2',6'-diethylacetanilide (common namebutachlor), the corresponding N-methoxy compound (common name alachlor),the corresponding N-iso-propyl compound (common name propachlor) and 3',4'-dichloropropionanilide (common name propanil);

P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile(common name dichlorobenil), 3,5-dibromo-4-hydroxybenzonitrile (commonname bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile (common nameioxynil).

Q. haloalkanoic herbicides such as 2,2-dichloropropionic acid (commonname dalapon), trichloroacetic acid (common name TCA) and salts thereof;

R. diphenylether herbicides such as 4-nitrophenyl2-nitro-4-trifluoromethylphenyl ether (common name fluorodifen), methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate (common name bifenox),2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid and2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ether;

S. N-(heteroarylaminocarbonyl)benzenesulfonamides such as2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide(commonly known as DPX 4189); and

T. miscellaneous herbicides including N,N-dimethyldiphenylacetamide(common name diphenamid), N-(1-naphthyl)phthalamic acid (common namenaptalam) and 3-amino-1,2,4-triazole.

Examples of useful contact herbicides include:

U. bipyridylium herbicides such as those in which the active entity isthe 1,1'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and thosein which the active entity is the 1,1'-ethylene-2,2'-dipyridylium ion(common name diquat);

V. organoarsenical herbicides such as monosodium methanearsonate (commonname MSMA); and

W. amino acid herbicides such as N-(phosphonomethyl)glycine (common nameglyphosate) and its salts and esters.

The invention is now illustrated by, but in no way limited to, thefollowing Examples.

EXAMPLE 12-[1-(Ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (7)

(i) An aqueous solution of 1% sodium hydroxide (29.5 ml) was addeddropwise over a period of 5 minutes to a suspension of mesityladehyde(10.0 g; 68 mmole) in acetone (50 ml) and water (50 ml). The mixture wasstirred at a temperature of 65° C. for a period of 11/2 hours and thenwas extracted with dichloromethane (200 ml). The organic extract waswashed several times with water, dried over anhydrous sodium sulfate,and the solvent was removed by evaporation under reduced pressure usinga rotary evaporator. The product1-(2,4,6-trimethylphenyl)but-1-en-3-one, a viscous oil, solidified onstanding to give a white solid (11.5 g; 90%), mp 64° C. Proton magneticresonance spectrum (CDCl₃ ; δ in ppm): 2.25 (12H, m); 6.30 (1H, d); 6.88(2H, s); 7.64 (1H, d).

(ii) Diethyl malonate (10.1 g; 60 mmole) was added to a solution ofsodium metal (1.4 g; 60 mmole) in anhydrous absolute ethanol (50 ml) andthe mixture was heated to reflux temperature. A mixture of1-(2,4,6-trimethylphenyl)but-1-en-3-one (11.4 g; 61 mmole) in anhydrousabsolute ethanol (50 ml) was added over a period of 2 minutes and themixture was heated under reflux for a period of 2 hours. An aqueoussolution of sodium hydroxide (7.3 g; 180 mmole in 100 ml of water) wasadded and the mixture was heated under reflux for a further 41/2 hours.The solution was poured into water (200 ml) and the aqueous mixture wasextracted twice with ethyl acetate (100 ml). The aqueous phase wasacidified with concentrated hydrochloric acid and warmed gently untilthe evolution of carbon dioxide ceased. The aqueous mixture wasextracted with ethyl acetate, dried over anhydrous sodium sulfate, andthe solvent was removed by evaporation under reduced pressure using arotary evaporator. The product, 3-hydroxy-5-mesitylcyclohex-2-en-1-one,was obtained as a pale yellow solid (10.9 g; 77.4%), mp 165° C. Protonmagnetic resonance spectrum (D₆ -dimethylsulfoxide; δ in ppm): 2.0-4.1(14H, m); 5.2 (1H, s); 6.8 (2H, s); 11.2 (1H, br.s.).

(iii) Propionic anhydride (15.0 ml) was added cautiously to freshlyprepared sodium methoxide (0.47 g; 9 mmole). On completion of thereaction 3-hydroxy-5-mesitylcyclohex-2-en-1-one (5.0 g; 22 mmole) wasadded and the reaction mixture was heated under reflux at a temperatureof 160° C. for a period of 2 hours. The excess propionic anhydride wasremoved by evaporation under reduced pressure using a rotary evaporator.Aqueous 30% sodium hydroxide solution (50 ml) was added to the residueand the mixture was heated under reflux for a period of 1 hour withvigorous stirring. After cooling the mixture was acidified withconcentrated hydrochloric acid and the aqueous mixture was extractedwith dichloromethane. The organic extracts were dried over anhydroussodium sulfate and the solvent was removed by evaporation under reducedpressure using a rotary evaporator. The product, a brown oil, waspurified by chromatography over silica gel (eluant dichloromethane) togive 3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one (3.17 g; 50.2%)as a pale yellow oil. Proton magnetic resonance spectrum (CDCl₃ ; δ inppm): 1.60 (3H, t, J=8 Hz); 2.24 (3H, s); 2.37 (6H, s); 2.64-5.26 (7H,m), 6.84 (2H, m); 18.26 (1H, s).

(iv) Ethoxyamine hydrochloride (0.45 g) and then aqueous 1% sodiumhydroxide (18.4 ml) were added to a solution of3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one (1.2 g; 4.2 mmole) inanhydrous absolute ethanol (200 ml). The mixture was stirred at roomtemperature for a period of 4 hours and then the ethanol was removed byevaporation under reduced pressure using a rotary evaporator. Theresidue was treated with dichloromethane and the organic phase waswashed twice with dilute aqueous hydrochloric acid and twice with water.The organic phase was dried over anhydrous sodium sulfate and thesolvent was removed by evaporation under reduced pressure to give theproduct,2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (1.25g; 93%), as a pale yellow oil.

The product was characterized by proton nuclear magnetic resonance andcarbon-13 nuclear magnetic resonance spectroscopy and spectroscopic datais recorded in Table 4, Example 21.

EXAMPLE 2

Compounds No 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 (see Table 1) wereprepared from the appropriate benzaldehyde derivative followingessentially the same procedure as that described in Example 1 in parts(i) to (iv). Each of the products was characterized by proton nuclearmagnetic resonance and/or carbon-13 nuclear magnetic resonancespectroscopy and spectroscopic data is recorded in Table 4, Example 21.

EXAMPLE 33-Benzoyloxy-2-[1-(ethoxyimino)propyl]-5-mesitylcyclohex-2-en-1-one (15)

(a) Aqueous 1% sodium hydroxide solution (6 ml) was added to a solutionof 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one(0.42 g; 1.28 mmole) in acetone (50 ml). The mixture was stirred at roomtemperature for a period of 5 minutes and then benzoyl chloride (0.2 g)was added dropwise. The mixture was stirred for a further period of 15minutes and then the solvent was removed by evaporation under reducedpressure using a rotary evaporator. The product was purified bychromatography over silica gel (eluant dichloromethane) to give3-benzoyloxy-2-[1-(ethoxyimino)propyl]-5-mesitylcyclohex-2-en-1-one(0.38 g; 68.6%) as a pale yellow oil.

(b) A solution of sodium hydroxide (0.12 g) in water (0.7 ml) was addeddropwise, with stirring, to a solution of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (0.89g) in tetrahydrofuran (9.5 ml). Benzoyl chloride (0.42 g) was addeddropwise, with stirring and the mixture was stirred at room temperaturefor a period of 30 minutes. The solvent was removed by evaporation underreduced pressure and the residue was taken up in dichloromethane andwater. The dichloromethane solution was separated, washed twice withwater, dried, and the solvent evaporated under reduced pressure. Theremaining oil was triturated with petroleum ether (b.p. 40°-60° C.) andthe solid which formed was recrystallised from isopropanol to give3-benzoyloxy-2-[1-(ethoxyimino)propyl]-5-mesitylcyclohex-2-en-1-one(0.79 g) as a solid m.p. 94°-95.5° C.

(c) A mixture of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (2.4g), anhydrous methyl ethyl ketone (25 ml) and anhydrous potassiumcarbonate (1.65 g) was treated dropwise, with stirring, with benzoylchloride (1.12 g). The mixture was heated under reflux with stirring fora period of 30 minutes and then filtered. The residue was washed withdiethyl ether and the solvent from the combined filtrate and washingswas evaporated under reduced pressure. The residue was taken up in ethylacetate and the solution was washed twice with water, dried, and thesolvent was evaporated under reduced pressure to give a dark brown oil.The oil was purified by chromatography on preparative thin layerchromatography plates (silica gel; eluent hexane/diethyl ether 75:25) togive 3-benzoyloxy-2-[1-(ethoxyimino)propyl]-5-mesitylcyclohex-2-en-1-one(1.9 g).

The product was cahracterized by proton nuclear magnetic resonancespectroscopy and spectroscopic data is recorded in Table 4, Example 21.

EXAMPLE 4

Compounds No 11, 12, 13, 14, 44, 45, 46, 48, 49, 50, 51, 58, 73, 81, 89,90, 91, 92, 93, 94 and 95 were prepared from compounds No 5, 5, 3, 1, 7,7, 7, 17, 24, 18, 16, 10, 62, 60, 7, 7, 7, 7, 7, 7, and 7 and theappropriate acid chloride (ethyl bromoacetate for compound no 95)following one of the procedures described in Example 3. Each of theproducts was characterized by proton nuclear magnetic resonancespectroscopy and spectroscopic data is recorded in Table 4, Example 21.

EXAMPLE 52-[1(Allyloxyimino)butyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (16)

(i) n-Butyryl chloride (2.3 g; 21.7 mmole) and then pyridine (1.7 g;21.7 mmole) were added to a stirred mixture of3-hydroxy-5-mesitylcyclohex-2-en-1-one (5.0 g; 21.7 mmole) anddichloromethane (50 ml) under a nitrogen atmosphere. The mixture wasstirred at room temperature for a period of two hours and then pouredinto slightly acidic water. The organic phase was separated and theaqueous phase was thoroughly extracted with dichloromethane. Thecombined organic phase and extracts were washed with water, dried overanhydrous magnesium sulfate and the solvent was removed by evaporationunder reduced pressure using a rotary evaporator. The residue wasdissolved in 1,2-dichloroethane (50 ml), stannic chloride (5.7 g; 22mmole) was added and the mixture was heated under reflux for a period of8 hours. The mixture was cooled and poured into water and the aqueousmixture was extracted several times with dichloromethane. The combinedorganic extracts were dried over anhydrous magnesium sulfate and thesolvent was removed by evaporation under reduced pressure using a rotaryevaporator. The residue was purified by chromatography over silica gel(eluant dichloromethane) to give2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one (2.4 g). Proton nuclearmagnetic resonance spectrum (CDCl₃ : δ in ppm): 1.01 (3H, t); 1.30-1.60(2H, m); 2.23 (3H, s); 2.37 (6H, s); 2.40-3.45 (7H, m); 6.83 (2H, s);18.24 (1H, s).

(ii) Allyloxyamine hydrochloride (0.72 g) and then a solution of sodiumhydroxide (0.25 g) in water (3 ml) were added to a stirred mixture of2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one (1.78 g; 5.9 mmole) and95% ethanol. The progress of the reaction was monitored using thin layerchromatography on silica gel (eluant dichloromethane). On completion ofthe reaction the ethanol was removed by evaporation using a rotaryevaporator and the residue was extracted with dichloromethane. Theorganic extract was washed with aqueous 5% hydrochloric acid and thenwith water and dried over anhydrous magnesium sulfate. The solvent wasremoved by evaporation under reduced pressure using a rotary evaporatorto give the product,2-[1-(allyloxyimino)butyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (1.6g) as an oil.

The product was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 4, Example21.

EXAMPLE 6

2-[1-(Ethoxyimino)butyl[-3-hydroxy-5-mesitylcyclohex-2-en-1-one (18) wasprepared from 2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one (seeExample 5 part (i)) and ethoxyamine hydrochloride following essentiallythe same procedure as that described in Example 1 part (iv). The productwas characterized by proton nuclear magnetic resonance spectroscopy andthe spectroscopic data is reported in Table 4, Example 21.

EXAMPLE 7

2-[1-(Allyloxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (17)was prepared from 3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one(see Example 1 parts (i) to (iii)) and allyloxyamine hydrochloridefollowing essentially the same procedure as that described in Example 5part (ii). The product was characterized by proton nuclear magneticresonance spectroscopy and the spectroscopic data is reported in Table4, Example 21.

EXAMPLE 82-[1-(Propoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (20)

(i) A mixture of 3-hydroxy-5-mesitylcyclohex-2-en-1-one (13.0 g, 0.056mole), propionic anhydride (26 ml) and propionic acid (26 ml) wasstirred and heated at 110° C. until homogeneous.Trifluoromethanesulphonic (0.5 ml) was added and the mixture was heatedat 110°-120° C. for 1 hour under an atmosphere of nitrogen. The mixturewas poured with stirring into ice-water, neutralized with sodiumbicarbonate and then extracted with diethyl ether. The ether extractgave the crude product as a brown oil which was purified bychromatography over silica gel (eluent dichloromethane) to give3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one (12.5 g, 77%) as anearly colourless solid, mp 86°-88° C.

(ii) 2-[1-(Propoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one(20) was prepared from3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one and propoxyaminehydrochloride following essentially the same procedure as that describedin Example 1 part (iv). The product was characterized by proton magneticresonance spectroscopy and the spectroscopic data is reported in Table4, Example 21.

EXAMPLE 9

Compounds No 19, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,35, 36, 37, 38, 39, 40, 41, 42, 52, 53, 54, 55, 56, 57, 60, 61, 62, 63,64, 65, 66, 67, 68, 69, 74, 75, 77, 79 and 82 were prepared from theappropriate 5-arylcyclohexane-1,3-dione (see Example 19), theappropriate carboxylic acid anydride/carboxylic acid mixture and theappropriate hydroxylamine hydrochloride derivative following essentiallythe same procedure as that described in Example 8. Each of the productswas characterized by proton nuclear magnetic resonance spectroscopy andappropriate physical data (melting point for solids and proton chemicalshift for liquids is recorded in Table 4, Example 21.

EXAMPLE 102-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(60)

(i) Sodium hydride (0.65 g, 0.027 mole) was added to a stirred solutionof 3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one (6.4 g, 0.024mole) in dimethylformamide (100 ml) at 60° C. After 15 minutes propionicanhydride (3.3 g, 0.027 mole) was added and the mixture was heated at110°-120° C. for 3 hours. It was then poured into water (300 ml) andextracted with diethyl ether (2×100 ml). The ether extracts were driedover anhydrous sodium sulfate and the solvent was removed by evaporationunder reduced pressure using a rotary evaporator. The product, a brownoil, was purified by chromatography over silica gel (eluent carbontetrachloride: chloroform (1:1)) to give3-hydroxy-5-(pentamethylphenyl)-2-propionyl-cyclohex-2-en-1-one (4.4 g,56%) as a nearly colourless solid, mp 84° C.

(ii)2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(60) was prepared from3-hydroxy-5-pentamethylphenyl-2-propionylcyclohex-2-en-1-one andethoxyamine hydrochloride following essentially the same procedure asthat described in Example 1 part (iv). The product was characterized byproton magnetic resonance spectroscopy and the spectroscopic data isreported in Table 4, Example 21.

EXAMPLE 11

Compounds No 71, 76, 80, 83 and 86 were prepared from the appropriate5-arylcyclohexane-1,3-dione (see Example 19), the appropriate carboxylicacid anhydride and the appropriate hydroxylamine hydrochloridederivative following essentially the same procedure as that described inExample 10. Each of the products was characterized by proton nuclearmagnetic resonance spectroscopy and spectroscopic data is recorded inTable 4, Example 21.

EXAMPLE 122-[1-(Ethoxyimino)ethyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(70)

(i) A mixture of 3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(3.00 g; see Example 19) acetic anhydride (10 ml) and acetic acid (10ml) was stirred and heated under reflux until homogeneous. p-Toluenesulfonic acid (0.5 g) was added and the mixture was refluxed for afurther 2 hours. After cooling the mixture was poured into water and thesolution was extracted with ether. The ether extract was washed severaltimes with water, dried over anhydrous magnesium sulfate and thenevaporated to dryness. The product, a brown oil, was purified by columnchromatography over silica gel (eluent dichloromethane) to give3-hydroxy-5-pentamethylphenyl-2-acetyl-cyclohex-2-en-1-one (1.50 g) as acrystalline solid, mp 183° C.

(ii)2-[1-(Ethoxyimino)ethyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(70) was prepared from3-hydroxy-5-pentamethylphenyl-2-acetyl-cyclohex-2-en-1-one andethoxyamine hydrochloride following essentially the same procedure asthat described in Example 1 part (iv). The product was characterized byproton magnetic resonance spectroscopy and the spectroscopic data isreported in Table 4, Example 21.

EXAMPLE 132-[1-(Ethoxyimino)benzyl]-3-hydroxy-5-(2,5-dimethylphenyl)cyclohex-2-en-1-one(87)

(i) Sodium hydride (0.53 g, 0.022 mole) was added to a stirred solutionof 3-hydroxy-5-(2,5-dimethylphenyl)cyclohex-2-en-1-one (4.32 g, 0.020mole; see Example 19) in dimethylformamide (60 ml) at 60° C. After 30minutes benzoic anhydride (5.00 g, 0.022 mole) was added and the mixturewas heated at 110°-120° C. for 4 hours. It was then poured into water(300 ml), acidified to pH 3 with hydrochloric acid and extracted withdiethyl ether (2×100 ml). The ether extracts were washed with water,dried over anhydrous sodium sulfate and evaporated under reducedpressure. The crude product, a brown oil, was dissolved in diethyl ether(200 ml), filtered, shaken with a saturated aqueous cupric acetatesolution (300 ml) and then the mixture was evaporated to dryness underreduced pressure. The crude solid was collected, washed successivelywith hot water, cold water, diethyl ether and hexane, then air dried togive the copper salt of2-benzoyl-5-(2,5-dimethylphenyl)-3-hydroxy-cyclohex-2-en-1-one (6.00 g)as a pale green solid mp 182°-185° C.

The copper salt, suspended in water, was acidified with 3N hydrochloricacid and then extracted into diethyl ether. The ether extract was washedwith water, dried over anhydrous sodium sulfate and evaporated underreduced pressure to give2-benzoyl-5-(2,5-dimethylphenyl)-3-hydroxy-cyclohex-2-en-1-one (4.20 g,65%) as a pale yellow oil. Proton nuclear magnetic resonance spectrum(CDCl₃ : δ in ppm): 2.33 (6H, s); 2.45-2.90 (4H, m); 3.30-3.70 (1H, m);6.90-7.15 (3H, brs); 7.30-7.80 (3H, m); 8.00-8.30 (2H, m).

(ii)2-[1-(Ethoxyimino)benzyl]-3-hydroxy-5-(2,5-dimethylphenyl)cyclohex-2-en-1-one(87) was prepared from3-hydroxy-5-(2,5-dimethylphenyl)-2-benzoyl-cyclohex-2-en-1-one andethoxyamine hydrochloride following essentially the same procedure asthat described in Example 1 part (iv). The product was characterized byproton magnetic resonance spectroscopy and the spectroscopic data isreported in Table 4, Example 21.

EXAMPLE 14 Sodium salt of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (43)

A solution of sodium hydroxide (0.45 g) in water (2 ml) was added to asolution of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one (3.86g) in acetone (50 ml). The solvent was removed under reduced pressureusing a rotary evaporator to yield the title compound as a yellow solid(3.98 g, 99%), mp 196° C. (decomp.).

EXAMPLE 15

Compounds No 47 and 59 (see Table 1) were prepared from the appropriate2-[1-(alkoxyiminopropyl]-3-hydroxy 5-(substitutedphenyl)cyclohex-2-en-1-one derivative and sodium hydroxide followingessentially the same procedure as that described in Example 11. Theproducts were characterized by mp data which is recoreded in Table 4,Example 21.

EXAMPLE 16 Copper salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(84)

2-[1-(Ethoxyimino)butyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(400 mg, 1.1 mmole) in diethyl ether (50 ml) was shaken with a saturatedaqueous cupric acetate solution (50 ml). The mixture was then evaporatedto dryness under reduced pressure. The solid residue was washedsuccessively with hot water, cooled water and diethyl ether, then driedto give the copper salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(390 mg, 88%) as a pale green solid, mp 210° C.

EXAMPLE 17

Nickel salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(pentamethylphenyl)cyclohex-2-en-1-one(85) was prepared following an analogous procedure to that described inExample 16. The product was obtained as a solid and its melting point isrecorded in Table 4, Example 21.

EXAMPLE 18 Tetrabutylammonium salt of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,4,6-trimethylphenyl)cyclohex-2-en-1-one(88)

To a solution of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,4,6-trimethylphenyl)cyclohex-2-en-1-one(329 mg; 10 mmole) in methanol (5 ml) was added a 25% methanolicsolution of tetra-n-butylammonium hydroxide (2.0 ml). The mixture waskept at room temperature for 3 hours and then evaporated to drynessunder reduced pressure using a rotary evaporator. The residue was takenup in dichloromethane (15 ml) and water (15 ml). The layers wereseparated and the organic layer washed with water (2×10 ml), dried overanhydrous sodium sulfate and evporated under reduced pressure to affordthe tetrabutylammonium salt of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,4,6-trimethylphenyl)cyclohex-en-1-one(340 mg), as a pale brown oil. The product was characterized by protonmagnetic resonance spectroscopy and the spectroscopic data is reportedin Table 4, Example 21.

EXAMPLE 19

The 5-arylcyclohexane-1,3-diones of formula IX used in the preparationof the compounds of formula I were prepared from the appropriatebenzaldehyde derivative following essentially the same procedure as thatdescribed in Example 1 parts (i) and (ii).

The majority of the 5-arylcyclohexane-1,3-diones of formula IX wereobtained as solids and were characterized by their nuclear magneticresonance spectra. For convenience, proton nuclear magnetic resonancespectroscopic (pmr) data is recorded in Table 2 below.

                  TABLE 2                                                         ______________________________________                                         ##STR9##                      IX                                             Compound                Proton Chemical Shift                                 (CH.sub.3).sub.n                                                                         Appearance   δ in ppm (D.sub.6 -DMSO)                        ______________________________________                                        2,3-(CH.sub.3).sub.2                                                                     yellow solid;                                                                              2.0-2.8 (10H,m); 3.4-3.7                                         mp 209° C.                                                                          (1H,m); 5.28 (1H,s); 7.00                                                     (3H,m); 11.2 (1H,brs)                                 2,4-(CH.sub.3).sub.2                                                                     yellow solid;                                                                              2.0-2.8 (10H,m); 3.40 (1H,                                       mp 167° C.                                                                          m); 5.25 (1H,s); 6.9-7.3                                                      (3H,m); 11.15 (1H,brs).                               2,5-(CH.sub.3).sub.2                                                                     pale yellow  2.0-3.8 (11H,m); 5.30                                            solid;       (1H,s); 6.8-7.3 (3H,m);                                          mp 180° C.                                                                          11.5 (1H,brs)                                         2,6-(CH.sub.3).sub.2                                                                     orange solid 2.0-3.8 (11H,m); 5.28                                                         (1H,s); 6.96 (3H,m); 11.2                                                     (1H,brs)                                              3,4-(CH.sub.3).sub.2                                                                     pale yellow  2.0-2.6 (11H,m); 5.25                                            solid;       (1H,s); 7.00 (3H,m); 11.0                                        mp 162° C.                                                                          (1H,brs)                                              3,5-(CH.sub.3).sub.2                                                                     yellow solid;                                                                              2.0-3.3 (11H,m); 5.25                                            mp 170° C.                                                                          (1H,s); 6.8-7.0 (3H,m);                                                       11.5 (1H,brs)                                         2,3,4-(CH.sub.3).sub.3                                                                   brown solid  2.0-2.7 (13H,m); 3.0-3.8                                                      (1H,m); 5.28 (1H,s);                                                          6.96 (2H,m); 11.2 (1H,brs)                            2,3,5-(CH.sub.3).sub.3                                                                   yellow solid;                                                                              2.20 (6H,s); 2.30 (3H,s);                                        mp 206° C.                                                                          2.3-3.0 (4H,m); 3.50 (1H,                                                     m); 5.25 (1H,s); 6.90                                                         (1H,s); 7.10 (1H,s);                                                          11.0 (1H,brs)                                         2,3,6-(CH.sub.3).sub.3                                                                   solid        1.9-3.1 (13H,m); 3.80                                                         (1H,m); 5.28 (1H,s); 6.91                                                     (2H,m); 11.3 (1H,brs)                                 2,4,5-(CH.sub.3).sub.3                                                                   brown solid; Not recorded                                                     mp 112° C.                                                  2,4,6-(CH.sub.3).sub.3                                                                   solid;       2.0-4.1 (14H,m); 5.20 (1H,                                       mp 165° C.                                                                          s); 6.80 (2H,s); 11.2                                                         (1H,brs)                                              3,4,5-(CH.sub.3).sub.3                                                                   colorless solid;                                                                           2.06 (3H,s); 2.20 (6H,s);                                        mp 206° C.                                                                          2.30-2.85 (4H,m); 308                                                         (1H,m); 5.28 (2H,s); 6.91                                                     (2H,s); 11.4 (1H,brs)                                 2,3,4,5-(CH.sub.3).sub.4                                                                 colorless solid;                                                                           Not recorded                                                     mp 223° C.                                                  2,3,4,6-(CH.sub.3).sub.4                                                                 yellow solid;                                                                              2.0-2.4 (12H,m); 2.4-3.2                                         mp 184° C.                                                                          (4H,m); 3.60 (1H,m); 5.25                                                     (1H,s); 6.80 (1H,s); 11.2                                                     (1H,brs)                                              2,3,4,5,6-(CH.sub.3).sub.5                                                               pale yellow  2.20 (12H,s); 2.4-3.2                                            solid;       (4H,m); 3.60 (1H,m); 5.25                                        mp 258° C.                                                                          (1H,s); 6.80 (1H,s); 11.2                                                     (1H,brs)                                              2,3,4,5,6- colorless    2.09 (3H,s); 2.11 (6H,s);                             (CH.sub.3).sub.5                                                                         solid;       2.20-2.50 (4H,m); 3.93                                           mp 235° C.                                                                          (1H,m); 5.15 (1H,s);                                                          11.0 (1H,brs)                                         ______________________________________                                    

EXAMPLE 20

The 2-acyl-5-arylcyclohexane-1,3-diones of formula XIII used in thepreparation of the compounds of formula I were prepared from thecorresponding 5-arylcyclohexane-1,3-dione of formula IX by acylationusing the appropriate acyl derivative following essentially the sameprocedure as that described in one of Examples 1 part (iii), 5 part (i),8 part (i), 10 part (i), 12 part (i) and 13 part (i).

The majority of the 2-acyl-5-arylcyclohexane-1,3-diones of formula XIIIwere obtained as oils and were characterized by their nuclear magneticresonance spectra. For convenience, proton nuclear magnetic resonancespectroscopic (pmr) data is recorded in Table 3 below.

                  TABLE 3                                                         ______________________________________                                         ##STR10##                    XIII                                            Compound               Proton Chemical Shift                                  (CH.sub.3).sub.n                                                                      R.sup.3 Appearance δ in ppm (CDCl.sub.3)                        ______________________________________                                        2,3-(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                       pale yellow                                                                              1.20 (3H,t); 2.25 (6H,                                             solid;     2×s); 2.3-4.0 (7H,m);                                        mp 100° C.                                                                        7.00 (3H,s); 18.20 (1H,s)                          2,4-(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                       orange oil 1.10 (3H,t); 2.30 (6H,s);                                                     2.4-3.0 (4H,m); 3.10                                                          (2H,q); 3.40 (1H,m);                                                          7.00 (3H,s); 18.10 (1H,s)                          2,5-(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                       oil        1.20 (3H,t); 2.25 (6H,s);                                                     2.40-3.80 (7H,m); 7.00                                                        (3H,m); 18.20 (1H,s)                               2,5-(CH.sub.3).sub.2                                                                  C.sub.6 H.sub.5                                                                       pale yellow                                                                              2.33 (6H,s); 2.45-2.90                                             oil        (4H,m); 3.30-3.70 (1H,m);                                                     6.90-7.15 (3H,brs); 7.30-                                                     7.80 (3H,m); 8.00-8.30                                                        (2H,m)                                             2,6-(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                       yellow oil 1.20 (3H,t); 2.40 (6H,s);                                                     2.4-4.0 (7H,m); 7.00                                                          (3H,s); 18.10 (1H,s)                               3,4-(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                       pale yellow                                                                              1.16 (3H,t); 2.24 (6H,s);                                          solid;     2.56-3.28 (7H,m); 6.96                                             mp 100° C.                                                                        (3H,m); 18.24 (1H,s)                               3,4-(CH.sub.3).sub.2                                                                  n-C.sub.3 H.sub.7                                                                     pale yellow                                                                              1.00 (3H,t); 1.65 (2H,m);                                          solid;     2.25 (6H,s); 2.5-3.3                                               mp 76° C.                                                                         (7H,m); 6.98 (3H,m);                                                          18.25 (1H,s)                                       3,5-(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                       yellow     1.10 (3H,t); 2.30 (6H,s);                                          solid;     2.5-3.4 (7H,m); 6.8-7.0                                            mp 113° C.                                                                        (3H,m); 18.20 (1H,s)                               2,3,4-  C.sub.2 H.sub.5                                                                       brown oil  1.20 (3H,t); 2.20 (9H,m);                          (CH.sub.3).sub.3           2.50-2.90 (4H,m); 3.10                                                        (2H,q); 3.60 (1H,m);                                                          6.95 (2H,m); 18.10 (1H,s)                          2,3,5-  C.sub.2 H.sub.5                                                                       yellow     1.20 (3H,t); 2.20 (3H,s);                          (CH.sub.3).sub.3                                                                              solid;     2.25 (6H,s); 2.45-3.20                                             mp 107° C.                                                                        (6H,m); 3.60 (1H,m);                                                          6.80 (1H,s) 6.85 (1H,s);                                                      18.20 (1H,s)                                       2,3,6-  C.sub.2 H.sub.5                                                                       orange     1.20 (3H,t); 2.25 (3H,s);                          (CH.sub.3).sub.3                                                                              oil        2.31 (3H,s); 2.37 (3H,s);                                                     2.5-3.4 (6H,m); 3.82 (1H,                                                     m); 6.94 (2H,m); 18.18                                                        (1H,s)                                             2,4,5-  C.sub.2 H.sub.5                                                                       yellow     1.20 (3H,t); 2.30 (9H,s);                          (CH.sub.3).sub.3                                                                              solid;     2.4-4.0 (7H,m); 7.00 (2H,                                          mp 111° C.                                                                        s); 18.20 (1H,s)                                   2,4,6-  CH.sub.3                                                                              colorless  2.24 (3H,s); 2.36 (6H,s);                          (CH.sub.3).sub.3                                                                              solid;     2.64 (3H,s); 2.65-4.00                                                        (5H,m); 6.84 (2H,s);                                                          18.17 (1H,s)                                       2,4,6-  C.sub.2 H.sub.5                                                                       solid;     1.60 (3H,t,J=8Hz); 2.24                            (CH.sub.3).sub.3                                                                              mp 86-88° C.                                                                      (3H,s); 2.37 (6H,s);                                                          2.64-5.26 (7H,m); 6.84                                                        (2H,m); 18.26 (1H,s)                               2,4,6-  n-C.sub.3 H.sub.7                                                                     oil        1.01 (3H,t); 1.30-1.60                             (CH.sub.3).sub.3           (2H,m); 2.23 (3H,s);                                                          2.37 (6H,s); 2.40-3.45                                                        (7H,m); 6.83 (2H,s);                                                          18.24 (1H,s)                                       3,4,5-  C.sub.2 H.sub.5                                                                       solid; mp  1.14 (3H,t); 2.14 (3H,s);                          (CH.sub.3).sub.3                                                                              93° C.                                                                            2.28 (6H,s); 2.3-3.4                                                          (7H,m); 6.79 (2H,s);                                                          18.12 (1H,s)                                       2,3,4,5-                                                                              C.sub.2 H.sub.5                                                                       pale yellow                                                                              1.15 (3H,t); 2.20 (12H,                            (CH.sub.3).sub.4                                                                              solid;     m); 2.40-2.90 (4H,m);                                              mp 97° C.                                                                         3.10 (2H,q); 3.55 (1H,                                                        m); 6.80 (1H,s); 18.10                                                        (1H,s)                                             2,3,4,6-                                                                              C.sub.2 H.sub.5                                                                       brown oil  1.20 (3H,t); 2.1-2.4                               (CH.sub.3).sub.4           (12H,4×S); 2.4-4.0 (7H,                                                 m); 6.90 (1H,s); 18.00                                                        (1H,s)                                             2,3,4,6-                                                                              n-C.sub.3 H.sub.7                                                                     brown oil  1.00 (3H,t); 1.65 (2H,m);                          (CH.sub.3).sub.4           2.1-2.4 (12H,4×s); 2.4-                                                 3.4 (6H,m); 3.80 (1H,m);                                                      6.80 (1H,s); 18.30 (1H,s)                          2,3,5,6-                                                                              C.sub.2 H.sub.5                                                                       brown oil  1.20 (3H,t); 2.30 (12H,                            (CH.sub.3).sub.4           s); 2.4-4.0 (7H,m);                                                           6.80 (1H,s); 18.00 (1H,s)                          2,3,4,5,6-                                                                            CH.sub.3                                                                              solid; mp  Not recorded                                       (CH.sub.3).sub.5                                                                              183° C.                                                2,3,4,5,6-                                                                            C.sub.2 H.sub.5                                                                       solid; mp  Not recorded                                       (CH.sub.3).sub.5                                                                              84° C.                                                 2,3,4,5,6-                                                                             -n-C.sub.3 H.sub.7                                                                   brown oil  1.00 (3H,t); 1.70 (2H,m);                          (CH.sub.3).sub.5           2.18 (9H,s); 2.25 (6H,s);                                                     2.25 (6H,s); 2.25-3.40                                                        (6H,m); 3.90 (1H,m);                                                          18.10 (1H,s)                                       ______________________________________                                    

EXAMPLE 21

The majority of the compounds of the invention were obtained as oils andwere characterized by, and can be identified by their nuclear magneticresonance spectra. For convenience proton nuclear magnetic resonancespectroscopic (pmr) data is recorded in Table 4a below and carbon-13nuclear magnetic resonance spectroscopic data is recorded in Table 4bbelow.

                  TABLE 4                                                         ______________________________________                                        Part (a)                                                                      Compound            Proton Chemical Shift                                     No      Appearance  δ in ppm (CDCl.sub.3)                               ______________________________________                                         1      Solid;      1.04-1.39 (6H,m); 2.28 (3H,s);                                    mp 70° C.                                                                          2.32 (3H,s); 2.63-4.01 (9H,m);                                                7.07 (3H,m); 15.03 (1H,br.s).                              2      Pale yellow 1.10-1.39 (6H,m); 2.28 (3H,s);                                    oil         2.31 (3H,s); 2.40-2.70 (4H,m);                                                2.97 (2H,q,J=8 Hz); 3.52 (1H,m);                                              4.10 (2H,q,J=8 Hz); 7.00-7.15                                                 (3H,m); 15.0 (1H,br.s).                                    3      Pale yellow 1.11-1.40 (6H,m); 2.31 (6H,s);                                    oil         2.64-3.02 (6H,m); 3.53 (1H,m);                                                4.12 (2H,q,J=8 Hz); 7.00-7.23                                                 (3H,m); 15.03 (1H,br,s).                                   4      Pale yellow 1.12-1.40 (6H,m); 2.41 (6H,s);                                    oil         2.62-3.14 (6H,m); 3.85 (1H,m);                                                4.12 (2H,q,J=8 Hz); 7.01 (3H,s);                                              15.03 (1H,br.s).                                           5      Pale yellow 1.10-1.37 (6H,m); 2.22 (6H,s);                                    oil         2.60-2.92 (7H,m); 4.07 (2H,q,                                                 J=8 Hz); 6.97-7.04 (3H,m);                                                    14.70 (1H,br.s).                                           6      Pale yellow 1.08-1.39 (6H,m); 2.30 (6H,s);                                    oil         2.65-3.00 (7H,m); 4.10 (2H,q,                                                 J=8 Hz); 6.85 (3H,s); 15.0 (1H,s).                          7     Pale yellow 1.13-1.48 (6H,m); 2.23 (3H,s);                                    oil         2.37 (6H,s); 2.60-4.23 (9H,m);                                                6.83 (2H,s); 14.99 (1H,s).                                 8      Pale yellow 1.07-1.40 (6H,m); 2.21 (6H,s);                                    oil         2.27 (3H,s); 2.36-3.07 (6H,m);                                                3.42 (1H,m); 4.10 (2H,q,J=8 Hz);                                              6.95-7.23 (2H,m); 15.0 (1H,br.s).                          9      Pale yellow 1.07-1.41 (6H,m); 2.23 (6H,s);                                    oil         2.27 (6H,s); 2.41-3.16 (6H,m);                                                4.00-4.12 (3H,m); 6.91 (1H,s);                                                15.0 (1H,br.s).                                           10      Pale yellow 1.07-1.41 (6H,m); 2.16 (3H,s);                                    oil         2.24 (3H,s); 2.32 (3H,s); 2.35                                                (3H,s); 2.40-3.35 (6H,m); 3.41-                                               4.07 (3H,m); 6.86 (1H,s); 15.0                                                (1H,br.s).                                                11      Pale yellow 0.92-1.74 (6H,m); 2.22 (6H,s);                                    oil         2.24-3.15 (7H,m); 3.99 (1H,q,                                                 J=8 Hz); 7.04-8.10 (8H,m).                                12      Pale yellow 0.90-1.34 (6H,m); 2.16 (3H,s);                                    oil         2.22 (6H,s); 2.24-3.15 (7H,m);                                                4.13 (2H,q,J=8 Hz); 7.00-7.25                                                 (3H,m).                                                   13      Pale yellow 1.10-1.39 (6H,m); 2.31 (6H,s);                                    oil         2.64-3.02 (6H,m); 3.53 (1H,m);                                                4.12 (2H,q,J=8 Hz); 7.00-7.23                                                 (3H,m); 7.38-8.10 (5H,m).                                 14      Pale yellow 1.04-1.39 (6H,m); 2.28 (3H,s);                                    oil         2.32 (3H,s); 2.63-4.01 (9H,m);                                                7.07 (3H,m); 7.38-8.08 (5H,m).                            15      Pale yellow 1.13-1.48 (6H,m); 2.24 (3H,s);                                    oil         2.42 (6H,s); 2.42-3.90 (9H,m);                                                6.85 (2H,s); 7.24-8.08 (5H,m).                            16      Pale yellow 1.05 (3H,t); 1.30-1.60 (2H,m);                                    oil         2.23 (3H,s); 2.37 (6H,s); 2.40-                                               3.90 (7H,m); 4.61 (2H,m); 5.34                                                (2H,m); 5.80 (1H,m); 6.80 (2H,s);                                             14.70 (1H,s).                                             17      Pale yellow 1.10 (3H,t); 2.21 (3H,s); 2.37                                    oil         (6H,s); 2.5-3.95 (8H,m); 4.52                                                 (2H,m); 5.34 (2H,m); 5.80 (1H,m);                                             6.80 (2H,s); 14.7 (1H,s).                                 18      Pale yellow 1.05 (3H,t); 1.32 (3H,t); 1.66                                    oil         (2H,m); 2.23 (3H,s); 2.37 (6H,s);                                             2.4-3.95 (7H,m); 4.15 (2H,q);                                                 6.83 (2H,s); 15.13 (1H,s).                                19      pale yellow 1.32 (3H,t); 2.23 (3H,s); 2.37                                    oil         (6H,s); 2.41 (3H,s); 2.4-4.0                                                  (5H,m); 4.12 (2H,q); 6.83 (2H,s);                                             14.7 (1H,s).                                              20      solid;      0.99 (3H,t); 1.21 (3H,t); 1.69                                    mp 114° C.                                                                         (2H,m); 2.23 (3H,s); 2.37 (6H,s);                                             2.3-3.9 (7H,m); 4.01 (2H,t);                                                  6.83 (2H,s); 14.99 (1H,s).                                21      solid;      0.95 (3H,t); 1.20 (3H,t); 1.2-1.8                                 mp 70-72° C.                                                                       (4H,m); 2.24 (3H,s); 2.37 (6H,s);                                             2.3- 3.9 (5H,m); 2.95 (2H,q); 4.06                                            (2H,t); 6.84 (2H,s); 15.05 (1H,s).                        22      solid;      1.19 (3H,t); 1.77 (3H,d,J=6 Hz);                                  mp 89-91° C.                                                                       2.24 (3H,s); 2.37 (6H,s); 2.3-3.9                                             (5H,m); 2.95 (2H,q); 4.47 (2H,d,                                              J=Hz); 5.6-5.9 (2H,m); 6.83 (2H,s),                                           14.9 (1H,s).                                              23      solid;      1.19 (3H,t); 2.24 (3H,s), 2.37                                    mp 69-71° C.                                                                       (6H,s); 2.3-3.9 (5H,m); 2.94                                                  (2H,q); 4.12 (2H,t); 5.0-5.3 (2H,                                             m); 5.6-6.0 (1H,m); 6.84 (2H,s);                                              14.8 (1H,brs).                                            24      pale yellow 1.19 (3H,t); 2.24 (3H,s); 2.37                                    oil         (6H,s); 2.4-3.9 (8H,m); 4.64 (2H,                                             d,J=2.4 Hz); 6.84 (2H,s); 13.90                                               (1H,s).                                                   25      pale yellow 1.20 (3H,t); 2.24 (3H,s); 2.37 (6H,                               oil         s); 2.4-3.9 (5H,m); 2.95 (2H,q);                                              4.10-4.20 (1H,m); 4.36-4.48 (2H,                                              m); 4.89-4.98 (1H,m); 6.84 (2H,                                               s); 14.06 (1H,brs).                                       26      pale yellow 1.22 (3H,t); 2.24 (3H,s); 2.38                                    oil         (6H,s); 2.4-3.9 (5H,m); 2.99                                                  (2H,q); 4.60 (2H,s); 5.47 (2H,s);                                             6.84 (2H,s); 14.5 (1H,brs).                               27      pale yellow 1.19 (3H,t); 2.23 (3H,s); 2.35                                    oil         (6H,s); 2.4-3.9 (5H,m), 2.90 (2H,                                             q); 5.06 (2H,s); 6.82 (2H,m); 7.36                                            (5H,m); 14.3 (1H,s).                                      28      pale yellow 1.18 (3H,t); 2.24 (3H,s); 2.36                                    oil         (6H,s); 2.4-3.9 (7H,m); 5.03 (2H,                                             s); 6.83 (2H,s); 7.33 (4H,s);                                                 14.16 (1H,s).                                             29      pale yellow 1.18 (3H,t); 2.24 (3H,s); 2.36                                    oil         (6H,s); 2.4-3.9 (7H,m); 5.02 (2H,                                             s); 6.83 (2H,s); 7.37 (4H,dofd);                                              14.5 (1H,s).                                              30      solid;      1.18 (3H,t); 2.24 (3H,s); 2.36                                    mp 68-70° C.                                                                       (6H,s); 2.3-3.9 (7H,m); 5.03 (2H,                                             s); 6.83 (2H,s); 7.0-7.4 (4H,m);                                              14.29 (1H,s).                                             31      pale yellow 1.18 (3H,t); 2.22 (3H,s); 2.34                                    oil         (9H,s); 2.3-3.9 (7H,m); 5.01 (2H,                                             s); 6.82 (2H,s); 7.21 (4H,dofd);                                              14.45 (1H,s).                                             32      solid;      1.21 (3H,t); 2.24 (3H,s); 2.35                                    mp <50° C.                                                                         (6H,s); 2.4-3.9-(7H,m); 5.18                                                  (2H,s); 6.83 (2H,s); 7.88 (4H,                                                dofd); 13.74 (1H,s).                                      33      pale yellow 1.20 (3H,t); 2.22 (3H,s); 2.34                                    oil         (6H,s); 2.4-3.9 (7H,m); 5.02 (2H,                                             s); 6.81 (2H,s); 7.2-7.34 (4H,m);                                             14.03 (1H,s).                                             34      solid;      1.20 (3H,t); 2.23 (3H,s); 2.35                                    mp <50°  C.                                                                        (6H,s); 2.4-3.9 (7H,m); 5.15 (2H,                                             s); 6.83 (2H,s); 7.19-7.40 (3H,m);                                            14.0 (1H,s).                                              35      solid;      0.9-1.2 (6H,m); 1.3-1.8 (6H,m);                                   mp 76° C.                                                                          2.25 (3H,s); 2.38 (6H,s); 2.4-3.9                                             (7H,m); 4.07 (2H,t); 6.84 (2H,s);                                             14 (1H,brs).                                              36      solid;      1.00 (3H,t); 1.5-1.8 (5H,m); 2.24                                 mp 68-70° C.                                                                       (3H,s); 2.37 (6H,s); 2.4-3.9 (7H,                                             m); 4.46 (2H,d,J=6 Hz); 5.4-6.0                                               (2H,m); 6.84 (2H,s); 14 (1H,brs).                         37      solid;      1.00 (3H,t); 1.3-1.6 (2H,m), 2.22                                 mp 70-71° C.                                                                       (3H,s); 2.36 (6H,s); 2.4-3.9                                                  (7H,m); 4.10 (2H,t); 5.0-5.3 (2H,                                             m); 5.6-6.0 (1H,m); 6.82 (2H,s);                                              14.6 (1H,s).                                              38      pale yellow 0.97 (3H,t); 1.6 (2H,m); 2.24 (3H,                                oil         s); 2.37 (6H,s); 2.4-3.7 (8H,m);                                              4.65 (2H,d,J=2.4 Hz); 6.84 (2H,s);                                            14.1 (1H,s).                                              39      pale yellow 1.00 (3H,t); 1.3-1.6 (2H,m); 2.24                                 oil         (3H,s); 2.38 (6H,s); 2.4-3.9 (7H,                                             m); 4.1-4.2 (1H,m); 4.36-4.51 (2H,                                            m); 4.89-4.98 (1H,m); 6.84 (2H,s);                                            14 (1H,brs).                                              40      solid;      1.00 (3H,t); 1.3-1.6 (2H,m);                                      mp 92-94°  C.                                                                      2.24 (3H,s); 2.37 (6H,s); 2.4-3.9                                             (7H,m); 4.59 (2H,s); 5.48 (2H,s);                                             6.84 (2H,s); 14 (1H,brs).                                 41      pale yellow 0.99 (3H,t); 1.4-1.7 (2H,m); 2.21                                 oil         (3H,s); 2.34 (6H,s); 2.4-3.9 (7H,                                             m); 5.00 (2H,s); 6.81 (2H,s); 7.30                                            (4H,s); 14.23 (1H,s).                                     42      pale yellow 0.99 (3H,t); 1.4-1.7 (2H,m); 2.23                                 oil         (3H,s); 2.35 (6H,s); 2.4-3.9 (7H,                                             m); 5.00 (2H,s); 6.83 (2H,s); 7.36                                            (4H,dofd); 14 (1H,brs).                                   43      pale yellow Not recorded                                                      solid,                                                                        mp 196° C.                                                             (decomp.)                                                             44      pale brown  0.90-1.20 (6H,m); 2.10 (3H,s);                                    solid;      2.30 (6H,s); 2.2-3.7 (6H,m); 3.99                                 mp 45-50° C.                                                                       (3H,m); 6.85 (2H,s); 8.10 (4H,                                                dofd).                                                    45      pale brown  1.0-1.2 (6H,m); 2.10 (3H,s); 2.30                                 solid,      (6H,s); 2.3-3.6 (6H,m); 3.99 (3H,                                 mp <50° C.                                                                         m); 6.80 (2H,s); 8.20 (4H,m).                             46      pale brown  1.0-1.3 (6H,m); 2.25 (3H,s); 2.45                                 solid;      (6H,s); 2.5-4.2 (9H,m); 6.80                                      mp 83° C.                                                                          (2H,s); 9.20 (3H,m).                                      47      yellow solid;                                                                             Not recorded                                                      mp 200° C.                                                             (decomp.)                                                             48      pale yellow 1.04 (3H,t); 2.24 (3H,s); 2.42                                    oil         (6H,s); 2.4-3.7 (5H,m); 4.46 (2H,                                             d,J=6 Hz); 5.12 (2H,m); 5.64 (1H,                                             m), 6.85 (2H,s); 7.2-8.1 (5H,m).                          49      Pale yellow 1.04 (3H,t); 2.22 (3H,s); 2.40                                    oil         (6H,s); 2.4-3.9 (7H,m); 4.55 (2H,                                             d,J=2.4 Hz); 6.82 (2H,s); 7.4-8.1                                             (5H,m).                                                   50      Pale orange 0.83-1.10 (6H,m); 1.53 (2H,m);                                    oil         2.23 (3H,s); 2.42 (6H,s); 2.4-3.7                                             (7H,m); 4.00 (2H,q,J=8 Hz); 6.84                                              (2H,s); 7.28-8.08 (5H,m).                                 51      orange oil  0.92 (3H,t); 1.53 (2H,m), 2.23                                                (3H,s); 2.42 (6H,s); 2.5-4.4 (7H,                                             m), 4.46(2H,d); 4.96 (2H,dofd);                                               5.77 (1H,m); 6.84 (2H,s); 7.2-8.1                                             (5H,m).                                                   52      pale brown  1.10 (3H,t); 1.25 (3H,t); 2.20                                    oil         (3H,s); 2.26 (6H,s); 2.4-3.7                                                  (5H,m); 2.96 (2H,q); 4.11 (2H,q);                                             6.99 (2H,s); 14.98 (1H,brs).                              53      yellow oil  1.10-1.40 (6H,2×t); 2.20 (3H,s);                                        2.26 (6H,s); 2.86-3.01 (6H,m);                                                3.56 (1H,m); 4.11 (2H,q); 6.89                                                (2H,s); 15.02 (1H,s).                                     54      pale yellow 1.17 (3H,t); 1.34 (3H,t); 2.15                                    oil         (3H,s); 2.28 (6H,s); 2.5-3.4                                                  (7H,m); 4.04 (2H,q); 6.87 (2H,s);                                             14.95 (1H,s).                                             55      yellow oil  0.92-1.40 (6H,m), 1.62 (2H,m);                                                2.16 (3H,s); 2.24 (3H,s); 2.32                                                (3H,s); 2.34 (3H,s); 2.6-3.0 (6H,                                             m); 3.74-4.23 (3H,m); 6.85 (1H,s);                                            15.1 (1H,s).                                              56      pale brown  1.19 (3H,t); 2.14 (3H,s); 2.24                                    oil         (3H,s); 2.32 (3H,s); 2.34 (3H,s);                                             2.4-3.14 (6H,m); 3.80 (1H,m);                                                 4.53 (2H,d,J=6 Hz); 4.35 (2H,m);                                              5.90 (1H,m); 6.83 (1H,s); 14.5                                                (1H,brs).                                                 57      yellow oil  0.97 (3H,t); 1.62 (2H,m); 2.13                                                (3H,s); 2.22 (3H,s); 2.29 (3H,s);                                             2.32 (3H,s); 2.60-3.02 (6H,m);                                                3.80 (1H,m); 4.51 (2H,d,J=6 Hz);                                              5.24 (2H,m); 5.80 (1H,m); 6.83                                                (1H,s); 14.65 (1H,s).                                     58      pale brown  0.99 (3H,t); 1.17 (3H,t); 2.17                                    oil         (3H,s); 2.25 (3H,s); 2.39 (3H,s);                                             2.49 (3H,s); 2.4-3.5 (6H,m);                                                  3.5-4.13 (3H,m); 6.87 (1H,s);                                                 7.25-7.56 (3H,m); 8.03-8.09 (2H,m)                        59      yellow solid                                                                              Not recorded                                                      mp 250° C.                                                             (decomp.)                                                             60      pale yellow 1.00-1.30 (6H,m); 2.10 (9H,s);                                    solid,      2.15 (6H,s); 2.2-3.3 (6H,m); 3.6-                                 mp 121° C.                                                                         4.15 (3H,m); 14.80 (1H,s).                                61      pale yellow 1.21 (3H,t); 2.14 (9H,s); 2.32                                    solid;      (6H,s); 2.43-3.86 (6H,m); 4.00                                    mp <50° C.                                                                         (1H,m); 4.50 (2H,d,J=7 Hz); 5.37                                              (2H,m); 5.89 (1H,m); 14.53 (1H,s).                        62      pale brown  1.00-1.32 (6H,2×t); 1.62 (2H,m);                            solid;      2.22 (9H,s); 2.32 (6H,s); 2.4-3.1                                 mp 116° C.                                                                         (6H,m); 3.99-4.23 (3H,m); 15.06                                               (1H,s).                                                   63      pale brown  1.00 (3H,t); 1.63 (2H,m); 2.21                                    oil         (9H,s); 2.31 (6H,s); 2.49-3.00                                                (6H,m); 4.00 (1H,m); 4.52 (2H,d,                                              J=7 Hz); 5.36 (2H,m); 5.88 (1H,m);                                            14.60 (1H,s).                                             64      yellow oil  1.04-1.40 (6H,2×t); 2.19-2.27                                           (12H,m); 2.67 (4H,m); 2.97 (2H,q);                                            3.59 (1H,m); 4.11 (2H,q); 6.87                                                (1H,s); 15.0 (1H,brs).                                    65      pale yellow 0.98 (3H,t); 1.18 (3H,t); 1.68                                    oil         (2H,m); 2.24 (6H,s); 2.5-3.4                                                  (7H,m); 4.00 (2H,t); 6.9-7.1                                                  (3H,m); 14 (1H,brs).                                      66      pale yellow 1.17 (3H,t); 2.25 (6H,s); 2.5-3.4                                 oil         7H,m); 4.54 (2H,d,J=6.4 Hz); 5.35                                             (2H,m); 5.90 (1H,m); 6.9-7.2 (3H,                                             m); 14.6 (1H,s).                                          67      pale yellow 0.98 (3H,t); 1.32 (3H,t); 1.6                                     oil         (2H,m); 2.25 (6H,s); 2.5-3.4 (7H,                                             m); 4.10 (2H,q); 7.00-7.25 (3H,m);                                            15.1 (1H,brs).                                            68      pale yellow 0.98 (6H,t); 1.63 (4H,m); 2.24                                    oil         (6H,s); 2.5-3.4 (7H,m); 4.01                                                  (2H,q); 6.95-7.25 (3H,m); 14 (1H,                                             brs).                                                     69      pale yellow 0.98 (3H,t); 1.63 (2H,m); 2.25                                    oil         (6H,s); 2.5-3.4 (7H,m); 4.52                                                  (2H,d,J=6.4 Hz); 5.25-5.44 (2H,m);                                            5.79-6.21 (1H,m); 6.90-7.25 (3H,                                              m); 14.6 (1H,s).                                          70      pale brown  1.32 (3H,t); 2.13-3.45 (23H,m);                                   solid;      4.13 (2H,q); 14.68 (1H,brs)                                       mp 183° C.                                                     71      pale yellow 1.12-1.40 (6H,m); 2.22 (3H,s);                                    oil         2.30 (3H,s); 2.38 (3H,s); 2.63-                                               2.99 (6H,m); 4.00-4.24 (3H,m);                                                5.93 (2H,m); 14.99 (1H,brs)                               72      solid;      Not recorded                                                      mp >250° C.                                                    73      pale yellow 0.92 (3H,t); 1.10 (3H,t); 1.48                                    oil         (2H,m); 2.23-3.76 (22H,m); 4.00                                               (2H,q); 7.45-8.09 (5H,m)                                  74      pale yellow 0.99 (3H,t); 1.60 (2H,m); 2.10-                                   oil         4.90 (23H,m); 6.85 (1H,s); 13.95                                              (1H,brs)                                                  75      pale brown  0.99 (3H,t); 1.63 (2H,m); 2.22-                                   solid;      4.94 (26H,m); 14.00 (1H,brs)                                      mp 132° C.                                                     76      oil         1.21 (3H,t); 2.22-4.89 (26H,m);                                               13.94 (1H,brs)                                            77      solid;      Not recorded                                                      mp 96° C.                                                      78      solid; mp   Not recorded                                                      >250° C.                                                       79      oil         0.99 (6H,2×t); 1.69 (4H,m); 2.22-                                       3.38 (22H,m); 4.02 (2H,t); 15.15                                              (1H,brs)                                                  80      oil         1.19 (3H,t); 2.22-2.83 (22H,m);                                               3.90 (3H,s); 14.71 (1H,brs)                               81      oil         1.09 (6H,2×t); 2.23-3.74 (22H,m);                                       4.02 (2H,q); 7.45-8.08 (5H,m)                             82      oil         1.01 (3H,t); 1.66 (2H,m); 2.23-4.06                                           (22H,m); 4.60 (2H,s); 5.48 (2H,s);                                            14.0 (1H,brs)                                             83      oil         1.20 (3H,t); 1.77 (3H,d); 2.23-                                               4.20 (22H,m); 4.47 (2H,d); 5.74                                               (2H,m); 14.0 (1H,brs)                                     84      pale green  Not recorded                                                      solid;                                                                        mp 210° C.                                                     85      pale brown  Not recorded                                                      solid;                                                                        mp 240° C.                                                     86      oil         1.22 (3H,t); 2.22-4.22 (25H,m);                                               5.12 (2H,s); 14.04 (1H,s)                                 87      pale brown  1.22 (3H,t); 2.31 (3H,s); 2.35-                                   oil         3.70 (5H,m); 3.95-4.45 (2H,m);                                                6.90-7.15 (3H,brs); 7.30-7.80 (3H,                                            m); 8.00-8.30 (2H,m)                                      88      pale brown  0.71-1.82 (34H,m); 2.22 (3H,s);                                   oil         2.36 (6H,s); 1.99-2.70 (4H,m);                                                2.76-4.27 (11H,m); 4.07 (2H,q);                                               6.78 (2H,s)                                               89      oil         0.8-1.4 (6H,m); 2.26 (3H,s); 2.45                                             (9H,s); 2.45-4.0 (9H,m); 6.92 (2H,                                            s); 7.34 (2H,d); 8.0 (2H,d)                               90      oil         0.7-1.4 (6H,m); 2.25 (12H,s); 2.37                                            (6H,s); 2.37-4.0 (9H,m); 6.85 (4H,                                            s)                                                        91      oil         0.8-1.3 (6H,m); 2.24 (3H,s); 2.42                                             (6H,s); 2.42-4.0 (12H,m+s); 6.85                                              (2H,s); 6.9 (2H,d); 7.95 (2H,d)                           92      oil         0.8-1.3 (6H,m); 2.24 (3H,s); 2.44                                             (6H,s); 2.45-4.2 (9H,m); 6.86 (2H,                                            s); 7.96 (2H,d); 7.44 (2H,d)                              93      oil         1.01 (3H,t); 1.27 (3H,t); 2.16 (3H,                                           s); 2.20 (3H,s); 2.38 (6H,s); 2.4-                                            4.3 (9H,m); 6.84 (2H,s)                                   94      oil         0.99 (3H,t); 1.23 (12H,s+t); 2.24                                             (3H,s); 2.40 (6H,s); 2.45-4.3                                                 (9H,m); 6.85 (2H,s)                                       95      solid; mp   0.9-1.4 (9H,m); 2.24 (3H,s); 2.38                                 138-142° C.                                                                        (6H,s); 2.4-4.2 (11H,m); 4.62                                                 (2H,s); 6.90 (2H,s)                                       ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Part (b)                                                                      Compound                                                                      No       Carbon-13 Chemical Shift δ in ppm (CDCl.sub.3)                 ______________________________________                                        1        11.26 (1C); 14.14 (1C); 14.68 (1C); 20.97 (2C);                               33.91 (1C); 39-45 (2C); 70.26 (1C); 107.10                                    (1C); 122.79 (1C); 125.85 (1C); 128.50 (1C);                                  134.03 (1C); 137.22 (1C); 140.20 (1C);                                        166.53 1C); 184-195 (2C).                                            2        11.22 (1C); 14.01 (1C); 19.07 (1C); 20.69 (1C);                               20.86 (1C); 33.32 (1C); 39-45 (2C); 70.21 (1C);                               107.05 (1C); 124.82 (1C); 126.99 (1C); 131.48                                 (1C); 135.22 (1C); 136.14 (1C); 137.39 (1C);                                  166.53 (1C); 184-195 (2C).                                           3        11.32 (1C); 14.19 (1C); 18.85 (1C); 21.07 (1C);                               21.18 (1C); 33.75 (1C); 39-45 (2C); 70.37 (1C);                               107.21 (1C); 125.85 (1C); 127.47 (1C); 130.78                                 (1C); 132.35 (1C); 135.02 (1C); 140.31 (1C);                                  166.59 (1C); 184-195 (2C).                                           4        11.27 (1C); 14.14 (1C); 21.13 (1C); 21.94 (2C);                               33.75 (1C); 39-45 (2C); 70.37 (1C); 107.21 (1C);                              126.77 (1C); 129.91 (2C); 136.36 (2C); 137.49                                 (1C); 166.75 (1C); 184-195 (2C).                                     5        11.32 (1C); 14.25 (1C); 19.34 (1C); 19.88 (1C);                               21.02 (1C); 37.38 (1C); 39-45 (2C); 70.26 (1C);                               107.48 (1C); 123.90 (1C); 128.07 (1C); 130.02                                 (1C); 135.17 (1C); 136.84 (1C); 140.15 (1C);                                  166.34 (1C); 184-195 (2C).                                           6        11.21 (1C); 14.09 (1C); 20.86 (2C); 21.29 (1C);                               37.54 (1C); 39-45 (2C); 70.26 (1C); 107.27 (1C);                              124.33 (2C); 128.56 (1C); 138.20 (2C); 142.42                                 (1C); 166.48 (1C); 184-195 (2C).                                     ______________________________________                                    

EXAMPLE 22

This non-limiting Example illustrates the preparation of formulations ofthe compounds of the invention.

(a) Emulsifiable Concentrate

Compound No 7 was dissolved in toluene containing 7% v/v "Teric" N13 and3% v/v "Kemmat" SC15B to give an emulsifiable concentrate which may bediluted with water to the required concentration to give an aqueousemulsion which may be applied by spraying.

("Teric" is a Trade Mark and "Teric" N13, is a product of ethoxylationof nonylphenol; "Kemmat" is a Trade Mark and "Kemmat" SC15B is aformulation of calcium dodecylbenzenesulfonate.)

(b) Aqueous Suspension

Compound No 7 (5 parts by weight) and "Dyapol" PT (1 part by weight) wasadded to an aqueous solution (94 parts by weight) of "Teric" N8 and themixture was ball milled to produce a stable aqueous suspension which maybe diluted with water to the required concentration to give an aqueoussuspension which may be applied by spraying. ("Dyapol" is a Trade Markand "Dyapol" PT is an anionic suspending agent; "Teric" N8 is a productof ethoxylation of nonylphenol.)

(c) Emulsifiable Concentrate

Compoiund No 7 (10 parts by weight), "Teric" N13 (5 parts by weight) and"Kemmat" SC15B (5 parts by weight) were dissolved in "Solvesso" 150 (80parts by weight) to give an emulsifiable concentrate which may bediluted with water to the required concentration to give an aqueousemulsion which may be applied by spraying. ("Solvesso" is a Trade Markand "Solvesso" 150 is a high boiling point aromatic petroleum fraction.)

(d) Dispersible Powder

Compound No 7 (10 parts by weight), "Matexil" DA/AC (3 parts by weight),"Aerosol" OT/B (1 part by weight) and china clay 298 (86 parts byweight) were blended and then milled to give a powder composition havinga particle size below 50 microns. ("Matexil" is a Trade Mark and"Matexil" DA/AC is the disodium salt of a naphthalenesulfonicacid/formaldehyde condensate; "Aerosol" is a Trade Mark and "Aerosol"OT/B is a formulation of the dioctyl ester of sodium sulfosuccinicacid.)

(e) High Strength Concentrate

Compound No 7 (99 parts by weight), silica aerogel (0.5 parts by weight)and synthetic amorphous silica (0.5 parts by weight) were blended andground in a hammer-mill to produce a powder having a particle size lessthan 200 microns.

(f) Dusting Powder

Compound No 7 (10 parts by weight), attapulgite (10 parts by weight) andpyrophyllite (80 parts by weight) were thoroughly blended and thenground in a hammer-mill to produce a powder of particle size less than200 microns.

Emulsifiable concentrates and/or suspensions of the compounds of theinvention were prepared essentially as described in part (a), (b) or (c)above and then diluted with water, optionally containing a surfaceactive agent and/or oil, to give aqueous compositions of the requiredconcentration which were used, as described in Examples 23 and 24, inthe evaluation of the pre-emergence and post-emergence herbicidalactivity of the compounds.

EXAMPLE 23

The pre-emergent herbicidal activity of the compounds of the inventionformulated as described in Example 22 was assessed by the followingprocedure:

The seeds of the test species were sown in rows 2 cm deep in soilcontained in seed boxes. The monocotyledonous plants and thedicotyledonous plants were sown in separate boxes and after sowing thetwo boxes were sprayed with the required quantity of a composition ofthe invention. Two duplicate seed boxes were prepared in the same mannerbut were not sprayed with a composition of the invention and were usedfor comparison purposes. All the boxes were placed in a glasshouse,lightly watered with an overhead spray to initiate germination and thensub-irrigated as required for optimum plant growth. After three weeksthe boxes were removed from the glasshouse and the effects of thetreatment was visually assessed. The results are presented in Table 5where the damage to plants is rated on a scale of from 0 to 5 where 0represents from 0 to 10% damage, 1 represents from 11 to 30% damage, 2represents from 31 to 60% damage, 3 represents from 61 to 80% damage, 4represents from 81 to 99% damage and 5 represents 100% kill. A dash (-)means that no experiment was carried out.

The names of the test plants are as follows:

Wh: Wheat

Ot: Wild Oats

Rg: Ryegrass

Jm: Japanese millet

P: Peas

Ip: Ipomea

Ms: Mustard

Sf: Sunflower

                  TABLE 5                                                         ______________________________________                                        PRE-EMERGENCE HERBICIDAL ACTIVITY                                             Com-                                                                          pound APPLICATION  TEST PLANT                                                 No    Rate (kg/ha) Wh     Ot  Rg  Jm   P   Ip  Ms  Sf                         ______________________________________                                         9    2.0          3      5   5   5    0   0   0   0                           9    0.5          0      5   5   5    0   0   0   0                          10    2.0          1      5   5   5    0   0   0   0                          10    0.5          0      5   5   5    0   0   0   0                          16    2.0          4      5   5   5    0   0   0   0                          16    0.5          0      5   5   5    0   0   0   0                          18    2.0          2      5   5   5    0   0   0   0                          18    0.5          0      5   5   4    0   0   0   0                          19    2.0          3      5   5   5    0   0   0   0                          19    0.5          0      3   5   5    0   0   0   0                          24    2.0          0      5   5   5    0   0   0   0                          24    0.5          0      0   5   5    0   0   0   0                          25    1.0          2      5   5   5    0   0   0   0                          25    0.25         1      1   5   5    0   0   0   0                          26    1.0          1      4   5   5    0   0   0   0                          26    0.25         0      0   5   5    0   0   0   0                          38    2.0          0      2   5   4    0   0   0   0                          38    0.5          0      3   5   4    0   0   0   0                          47    2.0          4      5   5   5    0   0   0   0                          47    0.5          0      0   5   4    0   0   0   0                          50    2.0          4      5   5   5    0   0   0   0                          50    0.5          0      4   5   4    0   0   0   0                          52    1.0          0      1   5   5    0   0   0   0                          52    0.25         0      0   4   0    0   0   0   0                          54    2.0          3      4   5   5    0   0   0   0                          54    0.5          0      0   5   5    0   0   0   0                          56    1.0          0      3   5   5    0   0   0   0                          56    0.25         0      2   5   5    0   0   0   0                          59    1.0          4      5   5   5    0   0   0   0                          59    0.25         2      5   5   5    0   0   0   0                          61    1.0          0      2   4   5    0   0   0   0                          61    0.25         0      0   5   4    0   0   0   0                          67    1.0          0      5   5   1    0   0   0   0                          67    0.25         0      0   5   0    0   0   0   0                          70    0.5          4      3   5   5    0   0   0   0                          70    0.125        0      1   5   5    0   0   0   0                          71    0.5          1      4   5   5    0   0   0   0                          71    0.125        0      1   5   5    0   0   0   0                          73    0.5          0      1   5   5    0   0   0   0                          74    0.5          0      3   5   5    0   0   0   0                          75    0.5          0      3   5   5    0   0   0   0                          76    0.5          0      2   5   5    0   0   0   0                          84    1.0          0      5   5   5    0   0   0   0                          ______________________________________                                    

EXAMPLE 24

The post-emergent herbicidal activity of the compounds of the inventionformulated as described in Example 22 was assessed by the followingprocedure.

The seeds of the test species were sown in rows 2 cm deep in soilcontained in seed boxes. The monocotyledonous plants and thedicotyledonous plants were sown in separate seed boxes in duplicate. Thefour seed boxes were placed in a glasshouse, lightly watered with anoverhead spray to initiate germination and then sub-irrigated asrequired for optimum plant growth. After the plants had grown to aheight of about 10 to 12.5 cm one box of each of the monocotyledonousplants and the dicotyledonous plants was removed from the glasshouse andsprayed with the required quantity of a composition of the invention.After spraying the boxes were returned to the glass house for a further3 weeks and the effect of treatment was visually assessed by comparisonwith the untreated controls. The results are presented in Table 6 wherethe damage to plants is rated on a scale of from 0 to 5 where 0represents from 0 to 10% damage, 1 represents from 11 to 30% damage, 2represents from 31 to 60% damage, 3 represents from 61 to 80% damage, 4represents from 81 to 99% damage and 5 represents 100% kill. A dash (-)means that no experiment was carried out.

The names of the test plants are as follows:

Wh: Wheat

Ot: Wild Oats

Rg: Ryegrass

Jm: Japanese millet

P: Peas

Ip: Ipomea

Ms: Mustard

Sf: Sunflower

                  TABLE 6                                                         ______________________________________                                        POST-EMERGENCE HERBICIDAL ACTIVIIY                                            Com-                                                                          pound APPLICATION  TEST PLANT                                                 No    Rate (kg/ha) Wh     Ot   Rg  Jm  P   Ip  Ms  Sf                         ______________________________________                                         1    2.0          1      5    5   5   0   0   0   0                           1    0.5          0      3    4   4   0   0   0   0                           2    2.0          1      4    5   5   0   0   0   0                           2    0.5          0      2    4   5   0   0   0   0                           3    2.0          0      3    5   5   0   0   0   0                           5    2.0          3      2    5   5   0   0   0   0                           5    0.5          0      4    4   4   0   0   0   0                           6    2.0          3      5    5   5   0   0   0   0                           6    0.5          0      4    5   5   0   0   0   0                           7    2.0          2      5    5   5   0   0   0   0                           7    0.5          2      5    5   5   0   0   0   0                           7    0.25         0      5    5   5   0   0   0   0                           7    0.125        0      5    5   4   0   0   0   0                           8    2.0          1      5    5   5   0   0   0   0                           8    0.5          0      3    5   5   0   0   0   0                          11    2.0          0      4    5   5   0   0   0   0                          11    0.5          0      3    3   4   0   0   0   0                          15    2.0          1      5    5   5   0   0   0   0                          15    0.5          1      5    5   5   0   0   0   0                          15    0.25         0      4    5   5   0   0   0   0                          15    0.125        0      5    5   4   0   0   0   0                          16    2.0          4      5    5   5   0   0   0   0                          16    0.5          2      5    5   5   0   0   0   0                          18    2.0          5      5    5   5   0   0   0   0                          18    0.5          3      5    5   5   0   0   0   0                          19    2.0          4      5    5   5   0   0   0   0                          19    0.5          0      5    5   5   0   0   0   0                          22    1.0          0      5    5   5   0   0   0   0                          22    0.25         0      5    5   5   0   0   0   0                          24    2.0          3      5    5   5   0   0   0   0                          24    0.5          0      5    5   4   0   0   0   0                          25    1.0          2      5    5   5   0   0   0   0                          25    0.25         0      5    5   5   0   0   0   0                          26    1.0          0      5    5   5   0   0   0   0                          26    0.25         0      4    5   4   0   0   0   0                          28    1.0          0      5    5   5   0   0   0   0                          28    0.25         0      5    5   4   0   0   0   0                          36    1.0          2      5    5   5   0   0   0   0                          36    0.25         0      5    5   5   0   0   0   0                          38    2.0          3      5    5   5   0   0   0   0                          38    0.5          1      5    4   4   0   0   0   0                          39    1.0          2      5    5   5   0   0   0   0                          39    0.25         0      5    5   5   0   0   0   0                          40    1.0          3      5    5   5   0   0   0   0                          40    0.25         0      5    5   5   0   0   0   0                          40    0.125        0      4    5   5   0   0   0   0                          41    1.0          0      5    5   5   0   0   0   0                          41    0.25         0      4    5   5   0   0   0   0                          46    1.0          4      5    5   5   0   0   0   0                          46    0.25         0      5    5   5   0   0   0   0                          47    2.0          3      5    5   5   0   0   0   0                          47    0.5          0      5    5   5   0   0   0   0                          50    2.0          4      5    5   5   0   0   0   0                          50    0.5          0      4    5   5   0   0   0   0                          51    2.0          4      5    5   5   0   0   0   0                          51    0.5          0      4    5   5   0   0   0   0                          52    1.0          0      5    5   5   0   0   0   0                          52    0.25         0      4    5   5   0   0   0   0                          53    1.0          0      5    5   5   0   0   0   0                          53    0.25         0      3    4   4   0   0   0   0                          54    2.0          2      5    5   5   0   0   0   0                          54    0.5          0      3    4   5   0   0   0   0                          55    0.25         5      5    5   5   0   0   0   0                          55    0.125        3      5    5   5   0   0   0   0                          57    0.25         1      5    5   5   0   0   0   0                          57    0.125        1      4    4   5   0   0   0   0                          58    1.0          4      5    5   5   0   0   0   0                          58    0.25         3      5    5   5   0   0   0   0                          59    1.0          5      5    5   5   0   0   0   0                          59    0.25         3      5    5   5   0   0   0   0                          60    2.0          5      5    5   5   0   0   0   0                          60    0.5          3      5    5   5   0   0   0   0                          61    1.0          3      5    5   5   0   0   0   0                          61    0.25         1      5    5   5   0   0   0   0                          62    1.0          5      5    5   5   0   0   0   0                          62    0.25         2      5    5   5   0   0   0   0                          62    0.125        1      5    5   5   0   0   0   0                          63    1.0          0      5    5   5   0   0   0   0                          63    0.25         0      4    4   4   0   0   0   0                          64    2.0          0      5    5   5   0   0   0   0                          64    0.5          1      5    5   5   0   0   0   0                          66    2.0          2      5    5   5   0   0   0   0                          66    0.5          0      5    5   5   0   0   0   0                          67    1.0          0      5    5   5   0   0   0   0                          67    0.25         0      4    4   4   0   0   0   0                          70    0.5          4      5    5   5   0   0   0   0                                0.125        0      4    3   5   0   0   0   0                          71    0.5          0      5    5   5   0   0   0   0                          71    0.125        0      3    5   5   0   0   0   0                          72    0.5          1      5    5   5   0   0   0   0                          72    0.125        0      5    5   5   0   0   0   0                          73    0.5          0      4    5   5   0   0   0   0                          73    0.125        0      4    5   5   0   0   0   0                          74    0.5          0      4/5  5   5   0   0   0   0                          74    0.125        0      4/5  5   5   0   0   0   0                          75    0.5          0      4    5   5   0   0   0   0                          75    0.125        0      3    4   5   0   0   0   0                          76    0.5          2      2    5   5   0   0   0   0                          76    0.125        0      0    5   5   0   0   0   0                          84    1            0      5    5   5   0   0   0   0                          84    0.125        0      2    1   0   0   0   0   0                          ______________________________________                                    

EXAMPLE 25

The compounds were formulated for test by mixing an appropriate amountwith 5 ml of an emulsion prepared by diluting 160 ml of a solutioncontaining 21.9 g per liter of "Span" 80 and 78.2 g per liter of "Tween"20 in methylcyclohexanone to 500 ml with water. "Span" 80 is a TradeMark for a surface-active agent comprising sorbitan monolaurate. "Tween"20 is a Trade Mark for a surface-active agent comprising a condensate ofsorbitan monolaurate with 20 molar proportions of ethylene oxide. Each 5ml emulsion containing a test compound was then diluted to 40 ml withwater and sprayed on to young pot plants (post-emergence test) of thespecies named in Table 7 below. Damage to test plants was assessed after14 days on a scale of 0 to 5 where 0 is 0 to 20% damage and 5 iscomplete kill. In a test for pre-emergence herbicidal activity, seeds ofthe test plants were sown in a shallow slit formed in the surface ofsoil in fibre trays. The surface was then levelled and sprayed, andfresh soil then spread thinly over the sprayed surface. Assessment ofherbicidal damage was carried out after 21 days using the same scale of0 to 5 as the post-emergence test. In both cases the degree ofherbicidal damage was assessed by comparison with untreated controlplants. The results are given in Table 7 below. A dash (-) means that noexperiment was carried out.

The names of the test plants were as follows:

Sb: Sugar beet

Rp: Rape

Ct: Cotton

Sy: Soy bean

Mz: Maize

Ww: Winter wheat

Rc: Rice

Sn: Senecio vulgaris

Ip: Ipomea purpurea

Am: Amaranthus retroflexus

Pi: Polygonum aviculare

Ca: Chenopodium album

Ga: Galium aparine

Xa: Xanthium pensylvanicum

Ab: Abutilon theophrasti

Co: Cassia obtusifolia

Av: Avena fatua

Dg: Digitaria sanguinalis

Al: Alopecurus myosuroides

St: Setaria viridis

Ec: Echinochloa crus-galli

Sh: Sorghum halepense

Ag: Agropyron repens

Cn: Cyperus rotundas

                                      TABLE 7                                     __________________________________________________________________________    PART A                                                                        Com-                                                                              APPLICATION                                                               pound                                                                             Method Rate                                                                            TEST PLANT                                                       No  (kg/ha)  Sb                                                                              Rp                                                                              Ct                                                                              Sy Mz Ww                                                                              Rc                                                                              Sn                                                                              Ip Am                                                                              Pi                                                                              Ca                                      __________________________________________________________________________    7   POST 1.9 0 0 0 --                                                                              5  3  4 0 0 -- 0 0                                       7   POST 0.5 0 0 0 --                                                                              5  0  4 0 1 -- 0 0                                       5   POST 2.0 --                                                                              --                                                                              --                                                                              --                                                                              -- 2  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      5   POST 1.0 --                                                                              --                                                                              --                                                                              --                                                                              -- 1  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      5   POST 0.5 --                                                                              --                                                                              --                                                                              --                                                                              -- 0  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      5   POST 0.25                                                                              --                                                                              --                                                                              --                                                                              --                                                                              -- 0  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      11  POST 2.0 --                                                                              --                                                                              --                                                                              --                                                                              -- 1  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      11  POST 1.0 --                                                                              --                                                                              --                                                                              --                                                                              -- 1  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      11  POST 0.5 --                                                                              --                                                                              --                                                                              --                                                                              -- 0  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      11  POST 0.25                                                                              --                                                                              --                                                                              --                                                                              --                                                                              -- 0  --                                                                              --                                                                              --                                                                              -- --                                                                              --                                      __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    PART B                                                                        Com-                                                                              APPLICATION                                                               pound                                                                             Method Rate                                                                            TEST PLANT                                                       No  (kg/ha)  Ga                                                                              Xa                                                                              Ab                                                                              Co                                                                              Av Dg Al                                                                              St                                                                              Ec                                                                              Sh                                                                              Ag                                                                              Cn                                       __________________________________________________________________________    7   POST 1.9 0 0 0 0 5  3  5 4 5 4 2 0                                        7   POST 0.5 0 0 0 0 4  3  4 5 5 3 0 0                                        5   POST 2.0 --                                                                              --                                                                              --                                                                              --                                                                              5  -- 4 5 --                                                                              --                                                                              --                                                                              --                                       5   POST 1.0 --                                                                              --                                                                              --                                                                              --                                                                              4  -- 4 4 --                                                                              --                                                                              --                                                                              --                                       5   POST 0.5 --                                                                              --                                                                              --                                                                              --                                                                              4  -- 4 3 --                                                                              --                                                                              --                                                                              --                                       5   POST 0.25                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4  -- 4 3 --                                                                              --                                                                              --                                                                              --                                       11  POST 2.0 --                                                                              --                                                                              --                                                                              --                                                                              5  -- 4 4 --                                                                              --                                                                              --                                                                              --                                       11  POST 1.0 --                                                                              --                                                                              --                                                                              --                                                                              4  -- 4 4 --                                                                              --                                                                              --                                                                              --                                       11  POST 0.5 --                                                                              --                                                                              --                                                                              --                                                                              4  -- 4 4 --                                                                              --                                                                              --                                                                              --                                       11  POST 0.25                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4  -- 4 3 --                                                                              --                                                                              --                                                                              --                                       __________________________________________________________________________

EXAMPLE 26

This Example illustrates the selective herbicidal activity of compoundsof the invention.

The compounds were formulated for test by mixing an appropriate amountwith 5 ml of an emulsion prepared by diluting 160 ml of a solutioncontaining 21.8 g per liter of "Span" 80 and 78.2 g per liter of "Tween"20 in methylcyclohexanone to 500 ml with water. "Span" 80 is a TradeMark for a surface-active agent comprising sorbitan monolaurate. "Tween"20 is a Trade Mark for a surface-active agent comprising a condensate orsorbitan monolaurate with 20 molar proportions of ethylene oxide. Each 5ml emulsion containing a test compound was then diluted to 40 ml withwater and sprayed on to young pot plants (post-emergence test) of thespecies named in Table 8 below. Damage to test plants was assessed after26 days on a scale of 0 to 9 where 0 is 0 to 10% damage and 9 iscomplete kill. The degree of herbicidal damage was assessed bycomparison with untreated control plants and the results are given inTable 8 below. A dash (-) means that no experiment was carried out.

The names of the test plants were as follows:

Ww: winter wheat

Br: spring barley

Av: Avena fatua

Al: Alopecurus myosuroides

St: Setaria viridis

                  TABLE 8                                                         ______________________________________                                        POST-EMERGENCE HERBICIDAL ACTIVITY                                            Compound APPLICATION  TEST PLANT                                              No       Rate (kg/ha) Ww      Br  Av    Al  St                                ______________________________________                                         5       0.10         0       0   9     8   6                                  5       0.20         1       1   9     9   8                                  5       0.40         0       1   9     9   9                                  7       0.03         0       1   8     8   8                                  7       0.04         0       0   9     9   8                                  7       0.08         1       1   --    --  --                                 7       0.16         0       1   --    --  --                                10       0.04         0       1   9     9   8                                 10       0.08         1       2   --    --  --                                10       0.16         2       5   --    --  --                                15       0.08         0       1   9     6   7                                 15       0.16         1       1   --    --  --                                15       0.32         1       0   --    --  --                                18       0.03         0       1   9     9   8                                 18       0.04         0       1   9     8   8                                 18       0.08         --      --  9     9   9                                 18       0.16         0       0   --    --  --                                60       0.04         --      --  9     8   9                                 60       0.06         0       6   9     8   9                                 60       0.08         0       5   9     8   9                                 60       0.16         0       8   --    --  --                                60       0.32         0       9   --    --  --                                62       0.02         --      --  9     7   9                                 62       0.04         --      --  9     9   9                                 62       0.06         0       5   9     9   9                                 62       0.08         0       7   9     9   9                                 62       0.16         0       9   --    --  --                                62       0.32         0       9   --    --  --                                72       0.04         --      --  9     9   9                                 72       0.06         0       0   9     9   9                                 72       0.08         0       3   9     9   9                                 72       0.16         0       7   --    --  --                                72       0.32         1       9   --    --  --                                78       0.04         --      --  9     7   8                                 78       0.06         0       0   9     8   9                                 78       0.08         0       2   9     9   9                                 78       0.16         0       7   --    --  --                                78       0.32         0       9   --    --  --                                ______________________________________                                    

We claim:
 1. A compound of the formula I ##STR11## wherein: R¹ isselected from the group consisting of: hydrogen; C₂ to C₆ alkanoyl;benzoyl and substituted benzoyl wherein the benzene ring is substitutedwith from 1 to 3 substituents selected from the group consisting ofhalogen, nitro, C₁ to C₆ alkyl and C₁ to C₆ alkoxy; and an inorganic ororganic cation selected from the alkali metal ions, the alkaline earthmetal ions, transition metal ions and the ammonium ion R⁴ R⁵ R⁶ R⁷N.sup.⊕ wherein R⁴, R⁵, R⁶ and R⁷ are independently selected from thegroup consisting of: hydrogen; C₁ to C₁₀ alkyl; and substituted C₁ toC₁₀ alkyl wherein the alkyl group is substituted with a substituentselected from the group consisting of hydroxy and C₁ to C₆ alkoxy;R² isselected from the group consisting of: C₁ to C₆ alkyl; C₂ to C₆ alkenyl;C₂ to C₆ alkynyl; C₁ to C₆ haloalkyl; C₂ to C₆ haloalkenyl; C₁ to C₆alkyl substituted with C₁ to C₆ alkoxy; C₁ to C₆ alkyl substituted withC₁ to C₆ alkylthio; and benzyl and substituted benzyl wherein thebenzene ring is substituted with from one to three substituents selectedfrom the group consisting of halogen, nitro and C₁ to C₆ alkyl; R³ isselected from the group consisting of C₁ to C₆ alkyl; and n is aninteger chosen from 0 to
 2. 2. A compound according to claim 1wherein:R¹ is selected from the group consisting of hydrogen, acetyl,butyryl, benzoyl, halobenzoyl, methylbenzoyl, methoxybenzoyl,nitrobenzoyl, trimethylbenzoyl, dinitrobenzoyl, the cations of thealkali metals sodium and potassium; the cations of the alkaline earthmetals magnesium, calcium and barium, the cations of the transitionmetals manganese, copper, zinc, iron, nickel, cobalt and silver, theammonium ion, and the tri- and tetra-alkyl ammonium ions wherein alkylis selected from C₁ to C₆ alkyl and C₁ to C₆ hydroxyalkyl; R² isselected from the group consisting of ethyl, n-propyl, n-butyl, allyl,propargyl, 2-fluoroethyl, 2-chloroallyl, methylthiomethyl, benzyl,halobenzyl, methylbenzyl and nitrobenzyl; R³ is selected from the groupconsisting of methyl ethyl and n-propyl; and n is an integer selectedfrom 0 to
 2. 3. A compound according to claim 2 wherein:R¹ is selectedfrom the group consisting of hydrogen, benzoyl and the cations of thealkali metals sodium and potassium; R² is selected from the groupconsisting of ethyl, n-propyl and allyl; R³ is selected from ethyl andn-propyl; and n is an integer selected from 0 to
 2. 4. A compoundaccording to claim 3 of formula ##STR12## wherein: R¹ is selected fromhydrogen, sodium and potassium;R² is selected from ethyl and allyl; andR³ is selected from ethyl and n-propyl.
 5. A compound according to claim3 of formula ##STR13## wherein: R¹ is selected from hydrogen, sodium andpotassium;R² is selected from ethyl and allyl; and R³ is selected fromethyl and n-propyl.
 6. A compound according to claim 3 of formula##STR14## wherein: R¹ is selected from hydrogen, sodium and potassium;R²is selected from ethyl and allyl; and R³ is selected from ethyl andn-propyl.
 7. A compound according to claim 3 selected from the groupconsistngof:2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one;2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,3,4,6-tetramethylphenyl)cyclohex-2-en-1-one;2-[1-(ethoxyimino)butyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one;2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1-one;2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1-one;2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1-onesodium salt; and2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1-onesodium salt.
 8. A herbicidal composition comprising as active ingredienta herbicidally effective amount of a compound as defined according toclaim 1 and a carrier therefor.
 9. A process for severely damaging orkilling unwanted plants which process comprises applying to said plants,or to the growth medium of said plants, an effective amount of acompound as defined according to claim
 1. 10. A process for selectivelycontrolling the growth of monocotyledonous weeds in dicotyledonous cropswhich process comprises applying to said crop, or to the growth mediumof said crop, a compound as defined according to claim 1 in an amountsufficient to severely damage or kill said weeds but insufficient tosubstantially damage said crop.
 11. A process for selectivelycontrolling the growth of monocotyledonous weeds in cultivated cropswhich process comprises applying to said crop or to the growth medium ofsaid crop a compound as defined according to claim 1 in an amountsufficient to severely damage or kill said weeds but insufficient tosubstantially damage said crop.
 12. A process according to claim 9wherein the compound is applied at a rate in the range of from 0.005 to20 kilograms per hectare.
 13. A process according to claim 10 whereinthe compound is applied at a rate in the range from 0.01 to 5 kilogramsper hectare.
 14. A process according to claim 11 wherein the compound isapplied at a rate in the range of from 0.01 to 5 kilograms per hectare.